Direct test of the equivalency of dynamic IR and dynamic Raman spectroscopies as techniques for observing ultrafast molecular dynamics

Andrea N. Giordano, Seth M. Morton, Lasse Jensen, Benjamin James Lear

Research output: Contribution to journalArticle

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Abstract

We report the temperature-dependent infrared (IR) and Raman spectra of Fe(CO)34-norbornadiene). This molecule undergoes carbonyl ligand site exchange on the vibrational time scale, and the effect of this exchange is observable as coalescence of the carbonyl bands in both the IR and Raman spectra. We outline a theory that we used to account for these effects and report simulations of the experimental spectra. We used these simulations to extract the carbonyl ligand exchange rates at various temperatures from the IR and Raman data. This data was used to calculate the activation energy for carbonyl exchange, yielding activation energies of 1.2 ± 0.2 and 1.4 ± 0.1 kcal/mol from the IR and Raman data, respectively. These activation energies are statistically identical and are consistent with previously reported values. This constitutes the first direct comparison between dynamic IR and Raman spectroscopies, and we find them to give identical results.

Original languageEnglish (US)
Pages (from-to)2067-2074
Number of pages8
JournalJournal of Physical Chemistry A
Volume117
Issue number10
DOIs
StatePublished - Mar 14 2013

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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