Picosecond studies of the temperature dependence of homogeneous and inhomogeneous vibrational linewidth broadening in liquid acetonitrile

S. M. George, Alex Harris, M. Berg, C. B. Harris

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

The temperature dependence of homogeneous and inhomogeneous vibrational linewidth broadening is reported for the symmetric CH3-stretching vibration in acetonitrile over its entire liquid range at P=1 atm. A selective excite-and-probe vibrational dephasing experiment based on transient stimulated Raman scattering in high laser depletion is used to measure the homogeneous dephasing times T2. The separation of homogeneous and inhomogeneous broadening processes is accomplished using the combined results of isotropic spontaneous Raman studies and selective picosecond vibrational dephasing experiments. As a function of temperature, the relative contributions of homogeneous and inhomogeneous broadening are shown to change significantly in opposing directions. Agreement between experiment and theory supports previous suggestions that homogeneous broadening is caused by rapidly varying processes which affect the vibration via short range repulsive forces. The results also suggest that inhomogeneous broadening is caused by slowly varying local density sites which interact with the vibration through long range attractive forces.

Original languageEnglish
Pages (from-to)83-94
Number of pages12
JournalJournal of Chemical Physics
Volume80
Issue number1
Publication statusPublished - 1984

Fingerprint

Linewidth
acetonitrile
vibration
temperature dependence
Liquids
liquids
Stimulated Raman scattering
Experiments
Temperature
Stretching
suggestion
depletion
Raman spectra
Lasers
probes
lasers
temperature
Direction compound

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Picosecond studies of the temperature dependence of homogeneous and inhomogeneous vibrational linewidth broadening in liquid acetonitrile. / George, S. M.; Harris, Alex; Berg, M.; Harris, C. B.

In: Journal of Chemical Physics, Vol. 80, No. 1, 1984, p. 83-94.

Research output: Contribution to journalArticle

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