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

7 Citations (Scopus)

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

Fingerprint

Raman spectroscopy
Molecular dynamics
molecular dynamics
activation energy
Infrared radiation
Activation energy
infrared spectra
Raman spectra
Raman scattering
ligands
Ligands
coalescing
Carbon Monoxide
simulation
Coalescence
infrared spectroscopy
Infrared spectroscopy
temperature
Temperature
Molecules

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

@article{232bcd505ebb49e281e1febe54d5c6c7,
title = "Direct test of the equivalency of dynamic IR and dynamic Raman spectroscopies as techniques for observing ultrafast molecular dynamics",
abstract = "We report the temperature-dependent infrared (IR) and Raman spectra of Fe(CO)3(η4-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.",
author = "Giordano, {Andrea N.} and Morton, {Seth M.} and Lasse Jensen and Lear, {Benjamin James}",
year = "2013",
month = "3",
day = "14",
doi = "10.1021/jp400696f",
language = "English (US)",
volume = "117",
pages = "2067--2074",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "10",

}

Direct test of the equivalency of dynamic IR and dynamic Raman spectroscopies as techniques for observing ultrafast molecular dynamics. / Giordano, Andrea N.; Morton, Seth M.; Jensen, Lasse; Lear, Benjamin James.

In: Journal of Physical Chemistry A, Vol. 117, No. 10, 14.03.2013, p. 2067-2074.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Direct test of the equivalency of dynamic IR and dynamic Raman spectroscopies as techniques for observing ultrafast molecular dynamics

AU - Giordano, Andrea N.

AU - Morton, Seth M.

AU - Jensen, Lasse

AU - Lear, Benjamin James

PY - 2013/3/14

Y1 - 2013/3/14

N2 - We report the temperature-dependent infrared (IR) and Raman spectra of Fe(CO)3(η4-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.

AB - We report the temperature-dependent infrared (IR) and Raman spectra of Fe(CO)3(η4-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.

UR - http://www.scopus.com/inward/record.url?scp=84875172101&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84875172101&partnerID=8YFLogxK

U2 - 10.1021/jp400696f

DO - 10.1021/jp400696f

M3 - Article

C2 - 23402708

AN - SCOPUS:84875172101

VL - 117

SP - 2067

EP - 2074

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 10

ER -