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.