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{{Electronic structure methods}}
 
'''Coupled cluster''' ('''CC''') is a numerical technique used for describing [[many-body system]]s.  Its most common use is as one of several  [[post-Hartree&ndash;Fock]] [[ab initio quantum chemistry methods|ab initio]] [[quantum chemistry]] methods in the field of [[computational chemistry]]. It essentially takes the basic [[Hartree&ndash;Fock]] [[molecular orbital]] method and constructs multi-electron wavefunctions using the exponential cluster operator to account for [[electronic correlation|electron correlation]]. Some of the most accurate calculations for small to medium sized molecules use this method.<ref>
{{cite book | first1 = H. G. |last1 =  Kümmel |chapter = A biography of the coupled cluster method | editor-first=R. F. | editor-last = Bishop  | editor2-first= T.  | editor2-last = Brandes
| editor3-first =  K. A. | editor3-last =  Gernoth | editor4-first =  N. R. |editor4-last = Walet |editor5-first = Y.
| title = Recent progress in many-body theories Proceedings of the 11th international conference| publisher =  World Scientific Publishing | location =  Singapore | year = 2002
| pages =334–348 | isbn= 978-981-02-4888-8 | editor5-last =Xian | displayauthors=5 }}
</ref><ref>{{cite book
  | last = Cramer  | first = Christopher J.
  | title = Essentials of Computational Chemistry
  | publisher = John Wiley & Sons, Ltd.  | year = 2002  | location = Chichester
  | pages = 191–232  | isbn = 0-471-48552-7}}</ref><ref>
{{Cite book|isbn=978-0-521-81832-2|publisher=Cambridge University Press |title=Many-Body Methods in Chemistry and Physics: MBPT and Coupled-Cluster Theory|year=2009| first1=Isaiah |last1=Shavitt | first2=Rodney J. | last2=Bartlett}}</ref>
 
The method was initially developed by [[Fritz Coester]] and [[Herman Kummel|Hermann Kümmel]] in the 1950s for studying [[nuclear physics]] phenomena, but became more frequently used when in 1966 [[Jiri Cizek|Jiři Čížek]] (and later together with [[Josef Paldus]]) reformulated the method for electron correlation in [[atoms]] and [[molecules]]. It is now one of the most prevalent methods in [[quantum chemistry]] that includes electronic correlation.
CC theory is simply the perturbative variant of the Many Electron Theory (MET) of [[Oktay Sinanoğlu]], which is the exact (and variational) solution of the many electron problem, so it was also called "Coupled Pair MET (CPMET)". J. Čížek used the correlation function of MET and used Goldstone type perturbation theory to get the energy expression while original MET was completely variational. Čížek first developed the Linear-CPMET and then generalized it to full CPMET in the same paper in 1966. He then also performed an application of it on benzene molecule with O. Sinanoğlu in the same year. Because MET is somewhat difficult to perform computationally, CC is simpler and thus, in today's computational chemistry, CC is the best variant of MET and gives highly accurate results in comparison to experiments.<ref>
{{cite journal | doi = 10.1063/1.1727484 | title = On the Correlation Problem in Atomic and Molecular Systems. Calculation of Wavefunction Components in Ursell-Type Expansion Using Quantum-Field Theoretical Methods | year = 1966 | last1 = Čížek | first1 = Jiří | journal = The Journal of Chemical Physics | volume = 45 | pages = 4256 |bibcode = 1966JChPh..45.4256C | issue = 11 }}</ref><ref>
{{cite book | last1 = Sinanoğlu | first1= O. | last2 = Brueckner | first2 =  K. | title = Three approaches to electron correlation in atoms
| publisher =  Yale Univ. Press | year = 1971| isbn=0-300-01147-4}} and references therein</ref><ref>
{{cite journal | doi = 10.1063/1.1732596 | title = Many-Electron Theory of Atoms and Molecules. I. Shells, Electron Pairs vs Many-Electron Correlations | year = 1962 | last1 = Si̇nanoğlu | first1 = Oktay | journal = The Journal of Chemical Physics | volume = 36 | pages = 706|bibcode = 1962JChPh..36..706S | issue = 3 }}</ref>
 
== Wavefunction ansatz ==
Coupled-cluster theory provides the exact solution to the time-independent Schrödinger equation
 
:<math>H\vert{\Psi}\rangle = E \vert{\Psi}\rangle </math>
 
where <math>H</math> is the [[Molecular Hamiltonian|Hamiltonian]] of the system, <math>\vert{\Psi}\rangle</math> the exact wavefunction, and ''E'' the exact energy of the ground state. Coupled-cluster theory can also be used to obtain solutions for [[excited state]]s using, for example, [[linear response coupled-cluster | linear-response]],<ref>{{cite journal | last1 = Monkhorst | first1 = H.J. | title = Calculation of properties with the coupled-cluster method | journal = International Journal of Quantum Chemistry | volume = 12, S11 | pages = 421 | year = 1977 | doi =10.1002/qua.560120850}}</ref> [[equation-of-motion coupled cluster| equation-of-motion]],<ref>{{cite journal |last1 = Stanton |first1 = John F. |last2 = Bartlett |first2 = Rodney J. |title = The equation of motion coupled-cluster method. A systematic biorthogonal approach to molecular excitation energies, transition probabilities, and excited state properties |journal = The Journal of Chemical Physics |volume = 98 |pages = 7029 |year = 1993 |doi = 10.1063/1.464746|bibcode = 1993JChPh..98.7029S |issue = 9 }}</ref> [[State-universal coupled cluster |state-universal multi-reference coupled cluster]],<ref>{{cite journal | last1 = Jeziorski | first1 = B. | last2 = Monkhorst | first2 = H. | title = Coupled-cluster method for multideterminantal reference states | journal = Physical Review A | volume = 24 | pages = 1668 | year = 1981 | doi = 10.1103/PhysRevA.24.1668|bibcode = 1981PhRvA..24.1668J | issue = 4 }}</ref> or [[valence-universal multi-reference coupled cluster]]<ref>{{cite journal | last1 = Lindgren | first1 = D. | last2 = Mukherjee | title = On the connectivity criteria in the open-shell coupled-cluster theory for general model spaces | journal = Physics Reports | volume = 151 | issue = 2| year = 1987 | doi = 10.1016/0370-1573(87)90073-1|bibcode = 1987PhR...151...93L | first2 = Debashis | pages = 93 }}</ref> approaches.
 
The wavefunction of the coupled-cluster theory is written as an exponential [[ansatz]]:
 
:<math> \vert{\Psi}\rangle = e^{T} \vert{\Phi_0}\rangle  </math>,
 
where <math>\vert{\Phi_0}\rangle</math>, the reference wave function, which is typically a [[Slater determinant]] constructed from [[Hartree&ndash;Fock]] [[molecular orbital]]s, though other wave functions such as [[Configuration interaction]], [[Multi-configurational self-consistent field]], or [[Brueckner orbitals]] can also be used. <math>T</math> is the cluster operator which, when acting on <math>\vert{\Phi_0}\rangle</math>, produces a linear combination of excited determinants from the reference wave function (see section below for greater detail).
 
The choice of the exponential ansatz is opportune because (unlike other ansätze, for example, [[configuration interaction]]) it guarantees the [[extensive quantity|size extensivity]] of the solution. [[Size consistency]] in CC theory, however, depends on the size consistency of the reference wave function.
 
A criticism of the method is that the conventional implementation employing the similarity-transformed Hamiltonian (see below) is not [[Variational principle|variational]], though there are bi-variational and quasi-variational approaches that have been developed since the first implementations of the theory. While the above ansatz for the wave function itself has no natural truncation, however, for other properties, such as energy, there is a natural truncation when examining expectation values, which has its basis in the linked- and connected-cluster theorems, and thus does not suffer from issues such as lack of size extensivity, like the variational configuration interaction.
 
== Cluster operator ==
 
The cluster operator is written in the form,
 
:<math>  T=T_1 + T_2 + T_3 + \cdots </math>,
 
where <math>T_1</math> is the operator of all single excitations, <math>T_2</math> is the operator of all double excitations and so forth. In the formalism of [[second quantization]] these excitation operators are expressed as
 
:<math>
T_1=\sum_{i}\sum_{a} t_{a}^{i} \hat{a}^{a}\hat{a}_{i},
</math>
 
:<math>
T_2=\frac{1}{4}\sum_{i,j}\sum_{a,b} t_{ab}^{ij} \hat{a}^{a}\hat{a}^{b}\hat{a}_j\hat{a}_{i},
</math>
 
and for the general n-fold cluster operator
 
<math>
T_n= \frac{1}{(n!)^{2}} \sum_{i_1,i_2,\ldots,i_n} \sum_{a_1,a_2,\ldots,a_n} t_{a_1,a_2,\ldots,a_n}^{i_1,i_2,\ldots,i_n} \hat{a}^{a_1} \hat{a}^{a_2} \ldots \hat{a}^{a_n} \hat{a}_{i_n} \ldots \hat{a}_{i_2} \hat{a}_{i_1}.
</math>
 
In the above formulae <math>(\hat{a}^{\dagger}_{a} =) \hat{a}^{a}</math> and <math>\hat{a}_{i}</math> denote the [[creation and annihilation operator]]s respectively and ''i, j'' stand for occupied (hole) and ''a, b'' for unoccupied (particle) orbitals (states). The creation and annihilation operators in the coupled cluster terms above are written in canonical form, where each term is in the [[normal order]] form, with respect to the Fermi vacuum, <math>\vert{\Phi_0}\rangle</math>. Being the one-particle cluster operator and the two-particle cluster operator, <math>T_1</math> and  <math>T_2</math> convert the reference function <math>\vert{\Phi_0}\rangle</math> into a linear combination of the singly  and doubly excited Slater determinants, respectively, if applied without the exponential (such as in [[Configuration interaction |CI]] where a linear excitation operator is applied to the wave function). Applying the exponential cluster operator to the wave function, one can then generate more than doubly excited determinants due to the various powers of <math>T_1</math> and <math>T_2</math> that appear in the resulting expressions (see below). Solving for the unknown coefficients <math>t_{a}^{i}</math> and <math>t_{ab}^{ij}</math> is necessary for finding the approximate solution <math>\vert{\Psi}\rangle</math>.
 
The exponential operator <math>e^{T}</math> may be expanded as a [[Taylor series]] and if we consider only the <math>T_1</math> and  <math>T_2</math> cluster operators of <math>T</math>, we can write:
 
:<math> e^{T} = 1 + T + \frac{1}{2!}T^2 + \cdots = 1 + T_1 + T_2 + \frac{1}{2}T_1^2 + T_1T_2 + \frac{1}{2}T_2^2 + \cdots </math>
 
Though this series is finite in practice because the number of occupied molecular orbitals is finite, as is the number of excitations, it is still very large, to the extent that even modern day massively parallel computers are inadequate, except for problems of a dozen or so electrons and very small basis sets, when considering all contributions to the cluster operator and not just <math>T_1</math> and  <math>T_2</math>. Often, as was done above, the cluster operator includes only singles and doubles (see CCSD below) as this offers a computationally affordable method that performs better than [[Møller–Plesset perturbation theory | MP2]] and CISD, but is not very accurate usually. For accurate results some form of triples (approximate or full) are needed, even near the equilibrium geometry (in the [[Franck–Condon principle | Franck-Condon]] region), and especially when breaking single-bonds or describing [[diradical]] species (these latter examples are often what is referred to as multi-reference problems, since more than one determinant has a significant contribution to the resulting wave function). For double bond breaking, and more complicated problems in chemistry, quadruple excitations often become important as well, though usually they are small for most problems, and as such, the contribution of <math>T_5</math>, <math>T_6</math> etc. to the operator <math>T</math> is typically small. Furthermore, if the highest excitation level in the <math>T</math> operator is ''n'',
 
:<math> T = T_1 + ... + T_n </math>
 
then Slater determinants for an ''N''-electron system excited more than ''n'' (< ''N'') times may still contribute to the coupled cluster wave function <math>\vert{\Psi}\rangle</math> because of the [[nonlinearity|non-linear]] nature of the exponential ansatz, and therefore, coupled cluster terminated at <math>T_n</math> usually recovers more correlation energy than CI with maximum ''n'' excitations.
 
== Coupled-cluster equations ==
 
The Schrödinger equation can be written, using the coupled-cluster wave function, as
 
:<math>H \vert{\Psi_{0}}\rangle = H e^{T} \vert{\Phi_0}\rangle = E e^{T} \vert {\Phi_0}\rangle </math>
 
where there are a total of ''q'' coefficients (''t''-amplitudes) to solve for. To obtain the ''q'' equations, first, we multiply the above Schrödinger equation on the left by <math> e^{-T} </math> and then project onto the entire set of up to ''m''-tuply excited determinants, where ''m'' is the highest order excitation included in <math>T</math>, that can be constructed from the reference wave function <math>\vert{\Phi_0}\rangle</math>, denoted by <math>\vert{\Phi^{*}}\rangle</math>, and individually, <math>\vert{\Phi_{i}^{a}}\rangle</math> are singly excited determinants where the electron in orbital ''i'' has been excited to orbital ''a''; <math>\vert{\Phi_{ij}^{ab}}\rangle</math> are doubly excited determinants where the electron in orbital ''i'' has been excited to orbital ''a'' and the electron in orbital ''j'' has been excited to orbital ''b'', etc. In this way we generate a set of coupled energy-independent non-linear algebraic equations needed to determine the ''t''-amplitudes.
 
:<math> \langle {\Phi_0}\vert e^{-T}He^{T} \vert{\Phi_0}\rangle = E \langle {\Phi_{0}}\vert  {\Phi_0}\rangle = E </math>
 
:<math> \langle {\Phi^{*}}\vert e^{-T}He^{T} \vert{\Phi_0}\rangle = E \langle {\Phi^{*}}\vert  {\Phi_0}\rangle = 0 </math>,
 
(note, we have made use of <math>e^{-T} e^{T}=1</math>, the identity operator, and we are also assuming that we are using orthogonal orbitals, though this does not necessarily have to be true, e.g., [[Valence bond theory | valence bond]] orbitals, and in such cases the last set of equations are not necessarily equal to zero) the latter being the equations to be solved and the former the equation for the evaluation of the energy.
 
Considering the basic CCSD method:
 
:<math>\langle {\Phi_0}\vert e^{-(T_1+T_2)}He^{(T_1+T_2)} \vert{\Phi_0}\rangle = E </math>,
:<math>\langle {\Phi_{i}^{a}}\vert e^{-(T_1+T_2)}He^{(T_1+T_2)} \vert{\Phi_0}\rangle =0</math>,
:<math>\langle {\Phi_{ij}^{ab}}\vert e^{-(T_1+T_2)}He^{(T_1+T_2)} \vert{\Phi_0}\rangle =0</math>,
 
in which the similarity transformed Hamiltonian, <math>\bar{H}</math>, can be explicitly written down using Hadamard's formula in Lie algebra, also called Hadamard's lemma (see also [[Baker–Campbell–Hausdorff formula]] (BCH formula), though note they are different, in that Hadamard's formula is a lemma of the BCH formula):
:<math> \bar{H} = e^{-T} H e^{T} = H + [H,T] + (1/2)[[H,T],T] + ... = (He^{T})_{C} </math>.
 
The subscript ''C'' designates the connected part of the corresponding operator expression.
 
The resulting similarity transformed Hamiltonian is non-Hermitian, resulting in different left- and right-handed vectors (wave functions) for the same state of interest (this is what is often referred to in coupled cluster theory as the biorthogonality of the solution, or wave function, though it also applies to other non-Hermitian theories as well).  The resulting equations are a set of non-linear equations which are solved in an iterative manner. Standard quantum chemistry packages ([[GAMESS (US)]], [[NWChem]], [[ACES (computational chemistry)|ACES II]], etc.) solve the coupled cluster equations using the [[Jacobi method]] and [[DIIS |  direct inversion of the iterative subspace (DIIS)]] extrapolation of the t-amplitudes to accelerate convergence.
 
== Types of coupled-cluster methods ==
 
The classification of traditional coupled-cluster methods rests on the highest number of excitations allowed in the definition of <math>T</math>. The abbreviations for coupled-cluster methods usually begin with the letters "CC" (for coupled cluster) followed by
 
# S - for single excitations (shortened to ''singles'' in coupled-cluster terminology)
# D - for double excitations (''doubles'')
# T - for triple excitations (''triples'')
# Q - for quadruple excitations (''quadruples'')
 
Thus, the <math>T</math> operator in CCSDT has the form
 
:<math> T = T_1 + T_2 + T_3.</math>
 
Terms in round brackets indicate that these terms are calculated based on [[perturbation theory]]. For example, the CCSD(T) method means:
 
# Coupled cluster with a full treatment singles and doubles.
# An estimate to the connected triples contribution is calculated non-iteratively using Many-Body Perturbation Theory arguments.
 
== General description of the theory ==
 
The complexity of equations and the corresponding computer codes, as well as the cost of the computation increases sharply with the highest level of excitation. For many applications CCSD, while relatively inexpensive, does not provide sufficient accuracy except for the smallest systems (approximately 2 to 4 electrons), and often times an approximate treatment of triples is needed. The most well known coupled cluster method that provides an estimate of connected triples is CCSD(T), which provides a good description of closed-shell molecules near the equilibrium geometry, but breaks down in more complicated situations such as bond breaking and diradicals. Another popular method that makes up for the failings of the standard CCSD(T) approach is CR-CC(2,3), where the triples contribution to the energy is computed from the difference between the exact solution and the CCSD energy, and is not based on perturbation theory arguments. More complicated coupled-cluster methods such as CCSDT and CCSDTQ are used only for high-accuracy calculations of small molecules. The inclusion of all ''n'' levels of excitation for the ''n''-electron system gives the exact solution of the [[Schrödinger equation]] within the given [[basis set]], within the Born&ndash;Oppenheimer approximation (although schemes have also been drawn up to work without the BO approximation<ref>{{cite journal | doi = 10.1103/PhysRevA.36.1544 | title = Chemical physics without the Born-Oppenheimer approximation: The molecular coupled-cluster method | year = 1987 | last1 = Monkhorst | first1 = Hendrik J | journal = Physical Review A | volume = 36 | pages = 1544–1561 | issue = 4 | pmid = 9899035}}</ref><ref>{{cite journal | doi = 10.1063/1.1528951 | title = Many-body effects in nonadiabatic molecular theory for simultaneous determination of nuclear and electronic wave functions: Ab initio NOMO/MBPT and CC methods | year = 2003 | last1 = Nakai | first1 = Hiromi | last2 = Sodeyama | first2 = Keitaro | journal = The Journal of Chemical Physics | volume = 118 | pages = 1119 | issue = 3}}</ref>).
 
One possible improvement to the standard coupled-cluster approach is to add terms linear in the interelectronic distances through methods such as CCSD-R12.  This improves the treatment of dynamical electron correlation by satisfying the [[Kato cusp]] condition and accelerates convergence with respect to the orbital basis set.  Unfortunately, R12 methods invoke the [[resolution of the identity]] which requires a relatively large basis set in order to be a good approximation.
 
The coupled-cluster method described above is also known as the ''[[single-reference]]'' (SR) coupled-cluster method because the exponential ansatz involves only one reference function <math>\vert{\Phi_0}\rangle</math>. The standard generalizations of the SR-CC method are the ''[[multi-reference]]'' (MR) approaches: [[state-universal coupled cluster]] (also known as [[Hilbert space]] coupled cluster), [[valence-universal coupled cluster]] (or [[Fock space]] coupled cluster) and [[state-selective coupled cluster]] (or state-specific coupled cluster).
 
== Historical accounts ==
In the first reference below, Kümmel comments:
 
:''Considering the fact that the CC method was well understood around the late fifties it looks strange that nothing happened with it until 1966, as Jiři Čížek published his first paper on a quantum chemistry problem. He had looked into the 1957 and 1960 papers published in ''Nuclear Physics'' by Fritz and myself. I always found it quite remarkable that a quantum chemist would open an issue of a nuclear physics journal. I myself at the time had almost gave up the CC method as not tractable and, of course, I never looked into the quantum chemistry journals. The result was that I learnt about Jiři's work as late as in the early seventies, when he sent me a big parcel with reprints of the many papers he and Joe Paldus had written until then.
 
[[Josef Paldus]] also wrote his first hand account of the origins of coupled-cluster theory, its implementation, and exploitation in electronic wave function determination; his account is primarily about the making of coupled-cluster theory rather than about the theory itself.<ref>{{cite book | last1 = Paldus | first1 = J. | chapter = The beginnings of coupled-cluster theory: an eyewitness account | editor-last = Dykstra | editor-first = C. | title = Theory and Applications of Computational Chemistry: The First Forty Years| pages = 115 | year = 2005 | publisher = Elsivier B.V.}}</ref>
 
== Relation to other theories ==
 
=== Configuration Interaction ===
The C<sub>j</sub> excitation operators defining the CI expansion of an N-electron system for the wave function <math>\vert{\Psi_0}\rangle</math>,
 
:<math>\vert{\Psi_0}\rangle = (1 + C)\vert{\Phi_0}\rangle</math>,
 
:<math>C = \sum_{j=1}^{N} C_{j}</math>,
 
are related to the cluster operators <math>T</math>, since in the limit of including up to <math>T_{N}</math> in the cluster operator the CC theory must be equal to full CI, we obtain the following relationships<ref>{{cite book | last1 = Paldus | first1 = J | title = Diagrammatic Methods for Many-Fermion Systems | year = 1981 | edition = Lecture Notes | location = University of Nijmegen, Njimegen, The Netherlands}}</ref><ref>{{cite book | last1 = Bartlett | first1 = R.J. | last2 = Dykstra | first2 = C.E. | last3 = Paldus | first3 = J. | title = Advanced Theories and Computational Approaches to the Electronic Structure of Molecules | editor-last = Dykstra | editor-first = C.E. | year = 1984 | pages = 127}}</ref>
 
:<math>C_{1} = T_{1}</math>,
 
:<math>C_{2} = T_{2} + \frac{1}{2}(T_{1})^{2}</math>,
 
:<math>C_{3} = T_{3} + T_{1}T_{2} + \frac{1}{6}(T_{1})^{3}</math>,
 
:<math>C_{4} = T_{4} + \frac{1}{2}(T_{2})^{2} + T_{1}T_{3} + \frac{1}{2}(T_{1})^{2}T_{2} + \frac{1}{24}(T_{1})^{4}</math>,
 
etc. For general relationships see J. Paldus, in ''Methods in Computational Molecular Physics'', Vol. 293 of ''Nato Advanced Study Institute Series B: Physics'', edited by S. Wilson and G.H.F. Diercksen (Plenum, New York, 1992), pp. 99-194.
 
=== Symmetry Adapted Cluster ===
The Symmetry adapted cluster (SAC)<ref>{{cite journal | last1 = Nakatsuji | first1 = H. | last2 = Hirao | first2 = K. | journal = Chemical Physics Letters | volume = 47 | issue = 3 | pages = 569 | year = 1977 | title = Cluster expansion of the wavefunction. Pseduo-orbital theory applied to spin correlation | doi = 10.1016/0009-2614(77)85042-2|bibcode = 1977CPL....47..569N }}</ref><ref>{{cite journal | last1 = Nakatsuji | first1 = H. | last2 = Hirao | first2 = K. | journal = Journal of Chemical Physics | volume = 68 | issue = 5 | pages = 2053 | year = 1978 | title = Cluster expansion of the wavefunction. Symmetry‐adapted‐cluster expansion, its variational determination, and extension of open‐shell orbital theory | doi = 10.1063/1.436028|bibcode = 1978JChPh..68.2053N }}</ref> approach determines the (spin and) symmetry adapted cluster operator
:<math>S = \sum_{I} S_{I}</math>
by solving the following system of energy dependent equations,
 
:<math>\langle\Phi\vert(H-E_{0})e^{S}\vert\Phi\rangle = 0</math>,
 
:<math>\langle\Phi_{i_{1}\ldots i_{n}}^{a_{1}\ldots a_{n}}\vert(H-E_{0})e^{S}\vert\Phi\rangle = 0</math>,
 
:<math>i_{1}<\cdots<i_{n}</math>, <math>a_{1}<\cdots<a_{n}</math>, <math>n=1,\dots,M_{s}</math>,
 
where <math>\vert\Phi_{i_{1}\ldots i_{n}}^{a_{1}\ldots a_{n}}\rangle</math> are the ''n''-tuply excited determinants relative to <math>\vert\Phi\rangle</math> (usually they are the spin- and symmetry-adapted configuration state functions, in practical implementations), and <math>M_{s}</math> is the highest-order of excitation included in the SAC operator. If all of the nonlinear terms in <math>e^{S}</math> are included then the SAC equations become equivalent to the standard coupled-cluster equations of Jiři Čížek. This is due to the cancellation of the energy-dependent terms with the disconnected terms contributing to the product of <math>He^{S}</math>, resulting in the same set of nonlinear energy-independent equations. Typically, all nonlinear terms, except <math>\frac{1}{2}S_{2}^{2}</math> are dropped, as higher-order nonlinear terms are usually small.<ref>{{cite journal | last1 = Ohtsuka | first1 = Y. | last2 = Piecuch | first2 = P. | last3 = Gour | first3 = J.R. | last4 = Ehara | first4 = M. | last5 = Nakatsuji | first5 = H. | journal = Journal of Chemical Physics | volume = 126 | issue = 16 | pages = 164111 | year = 2007 | title = Active-space symmetry-adapted-cluster configuration-interaction and equation-of-motion coupled-cluster methods for high accuracy calculations of potential energy surfaces of radicals | doi = 10.1063/1.2723121|bibcode = 2007JChPh.126p4111O | pmid = 17477593 }}</ref>
 
==See also==
* [[Quantum chemistry computer programs]]
 
== References ==
 
{{reflist}}
 
== External resources ==
 
[[Category:Quantum chemistry]]
[[Category:Electronic structure methods]]
[[Category:Post-Hartree–Fock methods]]

Revision as of 20:40, 5 May 2013

Template:Electronic structure methods

Coupled cluster (CC) is a numerical technique used for describing many-body systems. Its most common use is as one of several post-Hartree–Fock ab initio quantum chemistry methods in the field of computational chemistry. It essentially takes the basic Hartree–Fock molecular orbital method and constructs multi-electron wavefunctions using the exponential cluster operator to account for electron correlation. Some of the most accurate calculations for small to medium sized molecules use this method.[1][2][3]

The method was initially developed by Fritz Coester and Hermann Kümmel in the 1950s for studying nuclear physics phenomena, but became more frequently used when in 1966 Jiři Čížek (and later together with Josef Paldus) reformulated the method for electron correlation in atoms and molecules. It is now one of the most prevalent methods in quantum chemistry that includes electronic correlation. CC theory is simply the perturbative variant of the Many Electron Theory (MET) of Oktay Sinanoğlu, which is the exact (and variational) solution of the many electron problem, so it was also called "Coupled Pair MET (CPMET)". J. Čížek used the correlation function of MET and used Goldstone type perturbation theory to get the energy expression while original MET was completely variational. Čížek first developed the Linear-CPMET and then generalized it to full CPMET in the same paper in 1966. He then also performed an application of it on benzene molecule with O. Sinanoğlu in the same year. Because MET is somewhat difficult to perform computationally, CC is simpler and thus, in today's computational chemistry, CC is the best variant of MET and gives highly accurate results in comparison to experiments.[4][5][6]

Wavefunction ansatz

Coupled-cluster theory provides the exact solution to the time-independent Schrödinger equation

H|Ψ=E|Ψ

where H is the Hamiltonian of the system, |Ψ the exact wavefunction, and E the exact energy of the ground state. Coupled-cluster theory can also be used to obtain solutions for excited states using, for example, linear-response,[7] equation-of-motion,[8] state-universal multi-reference coupled cluster,[9] or valence-universal multi-reference coupled cluster[10] approaches.

The wavefunction of the coupled-cluster theory is written as an exponential ansatz:

|Ψ=eT|Φ0,

where |Φ0, the reference wave function, which is typically a Slater determinant constructed from Hartree–Fock molecular orbitals, though other wave functions such as Configuration interaction, Multi-configurational self-consistent field, or Brueckner orbitals can also be used. T is the cluster operator which, when acting on |Φ0, produces a linear combination of excited determinants from the reference wave function (see section below for greater detail).

The choice of the exponential ansatz is opportune because (unlike other ansätze, for example, configuration interaction) it guarantees the size extensivity of the solution. Size consistency in CC theory, however, depends on the size consistency of the reference wave function.

A criticism of the method is that the conventional implementation employing the similarity-transformed Hamiltonian (see below) is not variational, though there are bi-variational and quasi-variational approaches that have been developed since the first implementations of the theory. While the above ansatz for the wave function itself has no natural truncation, however, for other properties, such as energy, there is a natural truncation when examining expectation values, which has its basis in the linked- and connected-cluster theorems, and thus does not suffer from issues such as lack of size extensivity, like the variational configuration interaction.

Cluster operator

The cluster operator is written in the form,

T=T1+T2+T3+,

where T1 is the operator of all single excitations, T2 is the operator of all double excitations and so forth. In the formalism of second quantization these excitation operators are expressed as

T1=iataia^aa^i,
T2=14i,ja,btabija^aa^ba^ja^i,

and for the general n-fold cluster operator

Tn=1(n!)2i1,i2,,ina1,a2,,anta1,a2,,ani1,i2,,ina^a1a^a2a^ana^ina^i2a^i1.

In the above formulae (a^a=)a^a and a^i denote the creation and annihilation operators respectively and i, j stand for occupied (hole) and a, b for unoccupied (particle) orbitals (states). The creation and annihilation operators in the coupled cluster terms above are written in canonical form, where each term is in the normal order form, with respect to the Fermi vacuum, |Φ0. Being the one-particle cluster operator and the two-particle cluster operator, T1 and T2 convert the reference function |Φ0 into a linear combination of the singly and doubly excited Slater determinants, respectively, if applied without the exponential (such as in CI where a linear excitation operator is applied to the wave function). Applying the exponential cluster operator to the wave function, one can then generate more than doubly excited determinants due to the various powers of T1 and T2 that appear in the resulting expressions (see below). Solving for the unknown coefficients tai and tabij is necessary for finding the approximate solution |Ψ.

The exponential operator eT may be expanded as a Taylor series and if we consider only the T1 and T2 cluster operators of T, we can write:

eT=1+T+12!T2+=1+T1+T2+12T12+T1T2+12T22+

Though this series is finite in practice because the number of occupied molecular orbitals is finite, as is the number of excitations, it is still very large, to the extent that even modern day massively parallel computers are inadequate, except for problems of a dozen or so electrons and very small basis sets, when considering all contributions to the cluster operator and not just T1 and T2. Often, as was done above, the cluster operator includes only singles and doubles (see CCSD below) as this offers a computationally affordable method that performs better than MP2 and CISD, but is not very accurate usually. For accurate results some form of triples (approximate or full) are needed, even near the equilibrium geometry (in the Franck-Condon region), and especially when breaking single-bonds or describing diradical species (these latter examples are often what is referred to as multi-reference problems, since more than one determinant has a significant contribution to the resulting wave function). For double bond breaking, and more complicated problems in chemistry, quadruple excitations often become important as well, though usually they are small for most problems, and as such, the contribution of T5, T6 etc. to the operator T is typically small. Furthermore, if the highest excitation level in the T operator is n,

T=T1+...+Tn

then Slater determinants for an N-electron system excited more than n (< N) times may still contribute to the coupled cluster wave function |Ψ because of the non-linear nature of the exponential ansatz, and therefore, coupled cluster terminated at Tn usually recovers more correlation energy than CI with maximum n excitations.

Coupled-cluster equations

The Schrödinger equation can be written, using the coupled-cluster wave function, as

H|Ψ0=HeT|Φ0=EeT|Φ0

where there are a total of q coefficients (t-amplitudes) to solve for. To obtain the q equations, first, we multiply the above Schrödinger equation on the left by eT and then project onto the entire set of up to m-tuply excited determinants, where m is the highest order excitation included in T, that can be constructed from the reference wave function |Φ0, denoted by |Φ*, and individually, |Φia are singly excited determinants where the electron in orbital i has been excited to orbital a; |Φijab are doubly excited determinants where the electron in orbital i has been excited to orbital a and the electron in orbital j has been excited to orbital b, etc. In this way we generate a set of coupled energy-independent non-linear algebraic equations needed to determine the t-amplitudes.

Φ0|eTHeT|Φ0=EΦ0|Φ0=E
Φ*|eTHeT|Φ0=EΦ*|Φ0=0,

(note, we have made use of eTeT=1, the identity operator, and we are also assuming that we are using orthogonal orbitals, though this does not necessarily have to be true, e.g., valence bond orbitals, and in such cases the last set of equations are not necessarily equal to zero) the latter being the equations to be solved and the former the equation for the evaluation of the energy.

Considering the basic CCSD method:

Φ0|e(T1+T2)He(T1+T2)|Φ0=E,
Φia|e(T1+T2)He(T1+T2)|Φ0=0,
Φijab|e(T1+T2)He(T1+T2)|Φ0=0,

in which the similarity transformed Hamiltonian, H¯, can be explicitly written down using Hadamard's formula in Lie algebra, also called Hadamard's lemma (see also Baker–Campbell–Hausdorff formula (BCH formula), though note they are different, in that Hadamard's formula is a lemma of the BCH formula):

H¯=eTHeT=H+[H,T]+(1/2)[[H,T],T]+...=(HeT)C.

The subscript C designates the connected part of the corresponding operator expression.

The resulting similarity transformed Hamiltonian is non-Hermitian, resulting in different left- and right-handed vectors (wave functions) for the same state of interest (this is what is often referred to in coupled cluster theory as the biorthogonality of the solution, or wave function, though it also applies to other non-Hermitian theories as well). The resulting equations are a set of non-linear equations which are solved in an iterative manner. Standard quantum chemistry packages (GAMESS (US), NWChem, ACES II, etc.) solve the coupled cluster equations using the Jacobi method and direct inversion of the iterative subspace (DIIS) extrapolation of the t-amplitudes to accelerate convergence.

Types of coupled-cluster methods

The classification of traditional coupled-cluster methods rests on the highest number of excitations allowed in the definition of T. The abbreviations for coupled-cluster methods usually begin with the letters "CC" (for coupled cluster) followed by

  1. S - for single excitations (shortened to singles in coupled-cluster terminology)
  2. D - for double excitations (doubles)
  3. T - for triple excitations (triples)
  4. Q - for quadruple excitations (quadruples)

Thus, the T operator in CCSDT has the form

T=T1+T2+T3.

Terms in round brackets indicate that these terms are calculated based on perturbation theory. For example, the CCSD(T) method means:

  1. Coupled cluster with a full treatment singles and doubles.
  2. An estimate to the connected triples contribution is calculated non-iteratively using Many-Body Perturbation Theory arguments.

General description of the theory

The complexity of equations and the corresponding computer codes, as well as the cost of the computation increases sharply with the highest level of excitation. For many applications CCSD, while relatively inexpensive, does not provide sufficient accuracy except for the smallest systems (approximately 2 to 4 electrons), and often times an approximate treatment of triples is needed. The most well known coupled cluster method that provides an estimate of connected triples is CCSD(T), which provides a good description of closed-shell molecules near the equilibrium geometry, but breaks down in more complicated situations such as bond breaking and diradicals. Another popular method that makes up for the failings of the standard CCSD(T) approach is CR-CC(2,3), where the triples contribution to the energy is computed from the difference between the exact solution and the CCSD energy, and is not based on perturbation theory arguments. More complicated coupled-cluster methods such as CCSDT and CCSDTQ are used only for high-accuracy calculations of small molecules. The inclusion of all n levels of excitation for the n-electron system gives the exact solution of the Schrödinger equation within the given basis set, within the Born–Oppenheimer approximation (although schemes have also been drawn up to work without the BO approximation[11][12]).

One possible improvement to the standard coupled-cluster approach is to add terms linear in the interelectronic distances through methods such as CCSD-R12. This improves the treatment of dynamical electron correlation by satisfying the Kato cusp condition and accelerates convergence with respect to the orbital basis set. Unfortunately, R12 methods invoke the resolution of the identity which requires a relatively large basis set in order to be a good approximation.

The coupled-cluster method described above is also known as the single-reference (SR) coupled-cluster method because the exponential ansatz involves only one reference function |Φ0. The standard generalizations of the SR-CC method are the multi-reference (MR) approaches: state-universal coupled cluster (also known as Hilbert space coupled cluster), valence-universal coupled cluster (or Fock space coupled cluster) and state-selective coupled cluster (or state-specific coupled cluster).

Historical accounts

In the first reference below, Kümmel comments:

Considering the fact that the CC method was well understood around the late fifties it looks strange that nothing happened with it until 1966, as Jiři Čížek published his first paper on a quantum chemistry problem. He had looked into the 1957 and 1960 papers published in Nuclear Physics by Fritz and myself. I always found it quite remarkable that a quantum chemist would open an issue of a nuclear physics journal. I myself at the time had almost gave up the CC method as not tractable and, of course, I never looked into the quantum chemistry journals. The result was that I learnt about Jiři's work as late as in the early seventies, when he sent me a big parcel with reprints of the many papers he and Joe Paldus had written until then.

Josef Paldus also wrote his first hand account of the origins of coupled-cluster theory, its implementation, and exploitation in electronic wave function determination; his account is primarily about the making of coupled-cluster theory rather than about the theory itself.[13]

Relation to other theories

Configuration Interaction

The Cj excitation operators defining the CI expansion of an N-electron system for the wave function |Ψ0,

|Ψ0=(1+C)|Φ0,
C=j=1NCj,

are related to the cluster operators T, since in the limit of including up to TN in the cluster operator the CC theory must be equal to full CI, we obtain the following relationships[14][15]

C1=T1,
C2=T2+12(T1)2,
C3=T3+T1T2+16(T1)3,
C4=T4+12(T2)2+T1T3+12(T1)2T2+124(T1)4,

etc. For general relationships see J. Paldus, in Methods in Computational Molecular Physics, Vol. 293 of Nato Advanced Study Institute Series B: Physics, edited by S. Wilson and G.H.F. Diercksen (Plenum, New York, 1992), pp. 99-194.

Symmetry Adapted Cluster

The Symmetry adapted cluster (SAC)[16][17] approach determines the (spin and) symmetry adapted cluster operator

S=ISI

by solving the following system of energy dependent equations,

Φ|(HE0)eS|Φ=0,
Φi1ina1an|(HE0)eS|Φ=0,
i1<<in, a1<<an, n=1,,Ms,

where |Φi1ina1an are the n-tuply excited determinants relative to |Φ (usually they are the spin- and symmetry-adapted configuration state functions, in practical implementations), and Ms is the highest-order of excitation included in the SAC operator. If all of the nonlinear terms in eS are included then the SAC equations become equivalent to the standard coupled-cluster equations of Jiři Čížek. This is due to the cancellation of the energy-dependent terms with the disconnected terms contributing to the product of HeS, resulting in the same set of nonlinear energy-independent equations. Typically, all nonlinear terms, except 12S22 are dropped, as higher-order nonlinear terms are usually small.[18]

See also

References

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    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

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    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
  10. One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting

    In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang

    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
  11. One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting

    In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang

    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
  12. One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting

    In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang

    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
  13. 20 year-old Real Estate Agent Rusty from Saint-Paul, has hobbies and interests which includes monopoly, property developers in singapore and poker. Will soon undertake a contiki trip that may include going to the Lower Valley of the Omo.

    My blog: http://www.primaboinca.com/view_profile.php?userid=5889534
  14. 20 year-old Real Estate Agent Rusty from Saint-Paul, has hobbies and interests which includes monopoly, property developers in singapore and poker. Will soon undertake a contiki trip that may include going to the Lower Valley of the Omo.

    My blog: http://www.primaboinca.com/view_profile.php?userid=5889534
  15. 20 year-old Real Estate Agent Rusty from Saint-Paul, has hobbies and interests which includes monopoly, property developers in singapore and poker. Will soon undertake a contiki trip that may include going to the Lower Valley of the Omo.

    My blog: http://www.primaboinca.com/view_profile.php?userid=5889534
  16. One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting

    In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang

    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
  17. One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting

    In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang

    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
  18. One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting

    In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang

    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang