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'''Cavity ring-down spectroscopy''' ('''CRDS''') is a highly sensitive [[spectroscopy|optical spectroscopic]] technique that enables measurement of absolute [[optical extinction]] by samples that [[scattering|scatter]] and [[Absorption (electromagnetic radiation)|absorb]] light. It has been widely used to study gaseous samples which absorb light at specific [[wavelength]]s, and in turn to determine [[mole fraction]]s down to the [[parts per trillion]] level. The technique is also known as '''cavity ring-down laser absorption spectroscopy''' ('''CRLAS''').
 
A typical CRDS setup consists of a [[laser]] that is used to illuminate a high-finesse [[optical cavity]], which in its simplest form consists of two highly reflective [[mirror]]s. When the laser is in [[resonance]] with a cavity [[Normal mode|mode]], [[intensity (physics)|intensity]] builds up in the cavity due to [[constructive interference]]. The laser is then turned off in order to allow the measurement of the exponentially decaying light intensity leaking from the cavity. During this decay, light is reflected back and forth thousands of times between the mirrors giving an effective path length for the extinction on the order of a few kilometers.
 
If something that absorbs light is placed in the cavity, the amount of light decreases faster—it makes fewer bounces before it is all gone. A CRDS setup measures how long it takes for the light to decay to 1/''e'' of its initial intensity, and this "ringdown time" can be used to calculate the concentration of the absorbing substance in the gas mixture in the cavity.
 
==Detailed description==
 
Cavity ring down spectroscopy is a form of [[laser absorption spectroscopy]]. In CRDS, a laser pulse is trapped in a highly reflective (typically R > 99.9%) [[optical cavity|detection cavity]]. The intensity of the trapped pulse will decrease by a fixed percentage during each round trip within the cell due to both [[absorption (optics)|absorption]] and scattering by the medium within the cell and reflectivity losses.  The intensity of light within the cavity is then determined as an [[exponential function]] of time.
 
:<math>I(t) = I_0 \exp \left (- t / \tau \right)</math>
 
The principle of operation is based on the measurement of a decay rate rather than an absolute [[absorbance]]. This is one reason for the increased sensitivity over traditional absorption spectroscopy, as the technique is then immune to shot-to-shot laser fluctuations. The decay constant, τ, which is the time taken for the intensity of light to fall to 1/e of the initial intensity, is called the ring-down time and is dependent on the loss mechanism(s) within the cavity. For an empty cavity, the decay constant is dependent on mirror loss and various optical phenomena like scattering and refraction:
 
:<math>\tau_0 = \frac{n}{c} \cdot \frac{l}{1-R+X}</math>
 
where ''n'' is the [[index of refraction]] within the cavity, ''c'' is the [[speed of light]] in vacuum, ''l'' is the cavity length, ''R'' is the mirror reflectivity, and ''X'' takes into account other miscellaneous optical losses. This equation uses the approximation ln(1+''x'') ≈ ''x'' for ''x'' close to zero, which is the case under cavity ring-down conditionsOften, the miscellaneous losses are factored into an effective mirror loss for simplicity. An absorbing species in the cavity will increase losses according to the [[Beer-Lambert law]]. Assuming the sample fills the entire cavity,
 
:<math>\tau = \frac{n}{c} \cdot \frac{l}{1-R+X+ \alpha l }</math>
 
where α is the absorption coefficient for a specific analyte concentration. The decadic absorbance, ''A'', due to the analyte can be determined from both ring-down times.
 
:<math>A = \frac{n}{c} \cdot \frac{l}{2.303} \cdot \left ( \frac{1}{\tau} - \frac{1}{\tau_0} \right) </math>
 
Alternatively, the [[molar absorptivity]], ε, and analyte concentration, ''C'', can be determined from the ratio of both ring-down times. If ''X'' can be neglected, one obtains<br />
 
:<math>\frac{\tau_0}{\tau} =1+ \frac{ \alpha l }{1-R} =  1+\frac{ \epsilon l C}{2.303(1-R)}</math>
 
==Advantages of CRDS==
There are two main advantages to CRDS over other absorption methods:
 
First, it isn't affected by fluctuations in the laser intensity.  In most absorption measurements, the light source must be assumed to remain steady between blank (no [[analyte]]), standard (known amount of analyte), and sample (unknown amount of analyte).  Any drift (change in the light source) between measurements will introduce errors. In CRDS, the ringdown time does not depend on the intensity of the laser, so fluctuations of this type aren't a problem.  
 
Second, it is very sensitive due to its long pathlength.  In absorption measurements, the smallest amount that can be detected is proportional to the length that the light travels through a sample.  Since the light reflects many times between the mirrors, it ends up traveling long distances.  For example, a laser pulse making 500 round trips through a 1 meter cavity will effectively have traveled through 1 kilometer of sample.
 
Thus the advantages include:
*High sensitivity due to the multipass nature (i.e. long pathlength) of the detection cell.
*Immunity to shot variations in laser intensity due to the measurement of a rate constant.
*Wide range of use for a given set of mirrors; typically ±5% of the center wavelength.
*High throughput, individual ring down events occur on the millisecond time scale.
*No need for a fluorophore, which makes it more attractive than [[Laser Induced Fluorescence|LIF]] or [[REMPI]] for some (e.g. rapidly predissociating) systems.
 
==Disadvantages of CRDS==
*Spectra cannot be acquired quickly due to the [[monochromatic]] laser source which is used. Having said this, some groups are now beginning to develop the use of broadband [[LED]] or [[supercontinuum]] sources<ref>{{Cite journal |author=K. Stelmaszczyk et al. |journal=Appl. Phys. B-Lasers O. |volume=94 |date=2009 |page=369 |doi=10.1007/s00340-008-3320-z |title=Towards supercontinuum cavity ring-down spectroscopy |issue=3|bibcode = 2009ApPhB..94..369S }}</ref><ref>{{Cite journal |author=K. Stelmaszczyk et al. |journal=Opt. Express |volume=17 |date=2009 |page=3673 |doi=10.1364/OE.17.003673 |title=Cavity ring-down absorption spectrography based on filament-generated supercontinuum light |issue=5|bibcode = 2009OExpr..17.3673S }}</ref><ref>{{Cite journal |author=W. Nakaema et al. |journal=Sensors |volume=11 |date=2011 |page=1620 |doi=10.3390/s110201620 |title=PCF-Based Cavity Enhanced Spectroscopic Sensors for Simultaneous Multicomponent Trace Gas Analysis |issue=2}}</ref> for CRDS, the light of which can then be dispersed by a [[diffraction grating|grating]] onto a [[Charge-coupled device|CCD]], or [[Fourier transform]]ed spectrometer (mainly in broadband analogues of CRDS). Perhaps more importantly, the development of ICOS based techniques have now been demonstrated over the range from the near UV to the mid-infrared.{{Citation needed|date=September 2009}}
*Analytes are limited both by the availability of tunable laser light at the appropriate wavelength and also the availability of high reflectance mirrors at those wavelengths.
*Expense: the requirement for laser systems and high reflectivity mirrors often makes CRDS orders of magnitude more expensive than some alternative spectroscopic techniques.
 
==See also==
*[[Absorption spectroscopy]]
*[[Laser absorption spectrometry]]
*[[Noise-Immune Cavity-Enhanced Optical-Heterodyne Molecular Spectroscopy]] ([[NICE-OHMS]])
*[[TDLAS|Tunable Diode Laser Absorption Spectroscopy (TDLAS)]]
 
==References==
<references/>
* {{cite journal | title = Cavity ring-down Optical Spectrometer for absorption measurements using pulsed laser sources | journal = Review of Scientific Instruments | author = Anthony O'Keefe |coauthors=David A.G. Deacon | year = 1988 | volume = 59 | page = 2544|bibcode = 1988RScI...59.2544O |doi = 10.1063/1.1139895 }}
* {{cite journal | title = Cavity ring-down spectroscopy for quantitative absorption measurements | journal = The Journal of Chemical Physics | author = Piotr Zalicki |coauthors=Richard N. Zare | year = 1995 | volume = 102 | issue = 7 | date = 15 February 1995| pages = 2708–2717 | doi = 10.1063/1.468647 |bibcode = 1995JChPh.102.2708Z }}
* {{cite journal  | title = Cavity ring-down spectroscopy: Experimental schemes and applications | journal = International Reviews in Physical Chemistry | year = 2000 | volume = 19 | issue = 4 | author = Giel Berden |coauthors=Rudy Peeters; Gerard Meijer | doi = 10.1080/014423500750040627 | pages = 565–607 |bibcode = 2000IRPC...19..565B }}
 
{{DEFAULTSORT:Cavity Ring-Down Spectroscopy}}
[[Category:Spectroscopy]]

Revision as of 23:36, 23 October 2013

Cavity ring-down spectroscopy (CRDS) is a highly sensitive optical spectroscopic technique that enables measurement of absolute optical extinction by samples that scatter and absorb light. It has been widely used to study gaseous samples which absorb light at specific wavelengths, and in turn to determine mole fractions down to the parts per trillion level. The technique is also known as cavity ring-down laser absorption spectroscopy (CRLAS).

A typical CRDS setup consists of a laser that is used to illuminate a high-finesse optical cavity, which in its simplest form consists of two highly reflective mirrors. When the laser is in resonance with a cavity mode, intensity builds up in the cavity due to constructive interference. The laser is then turned off in order to allow the measurement of the exponentially decaying light intensity leaking from the cavity. During this decay, light is reflected back and forth thousands of times between the mirrors giving an effective path length for the extinction on the order of a few kilometers.

If something that absorbs light is placed in the cavity, the amount of light decreases faster—it makes fewer bounces before it is all gone. A CRDS setup measures how long it takes for the light to decay to 1/e of its initial intensity, and this "ringdown time" can be used to calculate the concentration of the absorbing substance in the gas mixture in the cavity.

Detailed description

Cavity ring down spectroscopy is a form of laser absorption spectroscopy. In CRDS, a laser pulse is trapped in a highly reflective (typically R > 99.9%) detection cavity. The intensity of the trapped pulse will decrease by a fixed percentage during each round trip within the cell due to both absorption and scattering by the medium within the cell and reflectivity losses. The intensity of light within the cavity is then determined as an exponential function of time.

The principle of operation is based on the measurement of a decay rate rather than an absolute absorbance. This is one reason for the increased sensitivity over traditional absorption spectroscopy, as the technique is then immune to shot-to-shot laser fluctuations. The decay constant, τ, which is the time taken for the intensity of light to fall to 1/e of the initial intensity, is called the ring-down time and is dependent on the loss mechanism(s) within the cavity. For an empty cavity, the decay constant is dependent on mirror loss and various optical phenomena like scattering and refraction:

where n is the index of refraction within the cavity, c is the speed of light in vacuum, l is the cavity length, R is the mirror reflectivity, and X takes into account other miscellaneous optical losses. This equation uses the approximation ln(1+x) ≈ x for x close to zero, which is the case under cavity ring-down conditions. Often, the miscellaneous losses are factored into an effective mirror loss for simplicity. An absorbing species in the cavity will increase losses according to the Beer-Lambert law. Assuming the sample fills the entire cavity,

where α is the absorption coefficient for a specific analyte concentration. The decadic absorbance, A, due to the analyte can be determined from both ring-down times.

Alternatively, the molar absorptivity, ε, and analyte concentration, C, can be determined from the ratio of both ring-down times. If X can be neglected, one obtains

Advantages of CRDS

There are two main advantages to CRDS over other absorption methods:

First, it isn't affected by fluctuations in the laser intensity. In most absorption measurements, the light source must be assumed to remain steady between blank (no analyte), standard (known amount of analyte), and sample (unknown amount of analyte). Any drift (change in the light source) between measurements will introduce errors. In CRDS, the ringdown time does not depend on the intensity of the laser, so fluctuations of this type aren't a problem.

Second, it is very sensitive due to its long pathlength. In absorption measurements, the smallest amount that can be detected is proportional to the length that the light travels through a sample. Since the light reflects many times between the mirrors, it ends up traveling long distances. For example, a laser pulse making 500 round trips through a 1 meter cavity will effectively have traveled through 1 kilometer of sample.

Thus the advantages include:

  • High sensitivity due to the multipass nature (i.e. long pathlength) of the detection cell.
  • Immunity to shot variations in laser intensity due to the measurement of a rate constant.
  • Wide range of use for a given set of mirrors; typically ±5% of the center wavelength.
  • High throughput, individual ring down events occur on the millisecond time scale.
  • No need for a fluorophore, which makes it more attractive than LIF or REMPI for some (e.g. rapidly predissociating) systems.

Disadvantages of CRDS

  • Spectra cannot be acquired quickly due to the monochromatic laser source which is used. Having said this, some groups are now beginning to develop the use of broadband LED or supercontinuum sources[1][2][3] for CRDS, the light of which can then be dispersed by a grating onto a CCD, or Fourier transformed spectrometer (mainly in broadband analogues of CRDS). Perhaps more importantly, the development of ICOS based techniques have now been demonstrated over the range from the near UV to the mid-infrared.Potter or Ceramic Artist Truman Bedell from Rexton, has interests which include ceramics, best property developers in singapore developers in singapore and scrabble. Was especially enthused after visiting Alejandro de Humboldt National Park.
  • Analytes are limited both by the availability of tunable laser light at the appropriate wavelength and also the availability of high reflectance mirrors at those wavelengths.
  • Expense: the requirement for laser systems and high reflectivity mirrors often makes CRDS orders of magnitude more expensive than some alternative spectroscopic techniques.

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

    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
  • 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
  • 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