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Time Resolved Absorption

Time resolved absorption spectroscopy is a technique used to analyze the lifetime and decay rate of unstable chemical intermediates with short lifetimes that are formed during chemical reactions. It works by using a short laser pulse to initiate a photochemical reaction in a sample, and then a pulsed light source probes the absorption of any transient species produced over time. The detected transient absorption signals are then analyzed to determine the decay rate and lifetime of the intermediate species.

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Vinod Kumar
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27 views

Time Resolved Absorption

Time resolved absorption spectroscopy is a technique used to analyze the lifetime and decay rate of unstable chemical intermediates with short lifetimes that are formed during chemical reactions. It works by using a short laser pulse to initiate a photochemical reaction in a sample, and then a pulsed light source probes the absorption of any transient species produced over time. The detected transient absorption signals are then analyzed to determine the decay rate and lifetime of the intermediate species.

Uploaded by

Vinod Kumar
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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TIMERESOLVEDABSORPTIONSPECTROSCOPY

Chemicalreactionsoftenproceedthroughasequenceofunstableintermediateslikeexcitedmolecules, molecularfragmentsorionizedmoleculesbeforeastableproductisformed.Theseintermediateshave veryshortlifetimeandcannotbeextractedfromthereactionmixtureandanalyzed.Timeresolved absorptionspectroscopyisaverygoodtechniquetoanalyzethelifetimeanddecayrateofthese intermediates.

BasicPrinciple:
Ashortpulseoflight(generallylaser)isusedtointeractwithasampleplacedintheopticalpathofthe spectrometer.Thisinteractionresultseitherinabsorptionoremissionprocess.Thechangeinthe detectorsignalwithtimecanbemeasuredandsignalchangemaybeduetoavarietyofprocessessuch aselectronicexcitationproducingatripletstate,cleavageofamoleculeproducingradicals,electron transfer,molecularrearrangementetc.Wemeasuretemporalchangeinabsorptionofthetransient speciesformedfollowinglaserexcitation.Thewavelengthoftheabsorptionmaximumisgenerallythe characteristicofthetransientspecies.Further,usingthistechniquewecanmeasurethedecayrateand lifetimeofthetransientspecies. Thedataobtainedisconvertedtoabsorbanceaccordingto:

A=log(I0/It)=log(I0/(I0Ia))=log(1(IAIB)/I0) Where A=absorbance

I0=analyzinglightlevel It=lighttransmittedbyanabsorbingsample Ia=lightabsorbedbyanabsorbingsample IA=digitizersignalcontainingtransientabsorptiondata IB=digitizersignalcontainingbaselinedata

OpticalScheme: AgeneralopticalschemefortheFlashPhotolysistechniqueisshowninthenext page.Thelaserisusedtoinitiatethephotochemistryandthetransientformedisprobedbywhitelight source(usuallypulsedlamp/laser).Bothexcitationsourceandmonitoringsourcemeetatthesampleat rightangleandthechangeintheabsorptionisdetectedbythedetector(usuallyphotomultipliertube). The transient signals were acquired and analysed with a combination of oscilloscope and a computer. In order to avoid the local heating the sample flow system is used to circulate the system.

TypicalsignalRecordedinFlashPhotolysisexperiment
Atypicaldecayplotisshownbelow.Singleormultiexponentialfitting(dependinguponthenumberof thetransientspeciesinvolved)areusedtofindoutthedecayrate.Inthecaseofthequenching experimentsthedecayrateisplottedagainsttheconcentrationofthequencher.Aftergetting acquaintedwiththeinstrumenttimeresolvedabsorptionexperimentisplannedtobecarriedout.

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