Inhomogeneous broadening of vibrational linewidths in polyatomic liquids

Journal Article · Mon Dec 01 04:00:00 EST 1980 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.440077· OSTI ID:7026251

George, S M; Auweter, H; Harris, C B

The first account of inhomogeneous broadening of vibrational linewidths in non-hydrogen-bonded liquids is presented based on the combined results of isotropic spontaneous Raman studies and picosecond coherent probing experiments. The symmetric CH/sub 3/-stretching vibrational linewidths studied were found to be inhomogeneously broadened to various degrees. A correlation between the inhomogeneous broadening and the liquid's local number density distribution width is demonstrated, upon which a theoretical model for inhomogeneous broadening is developed. A stochastic line shape theory is constructed in which homogeneous and inhomogeneous broadening are treated simultaneously in terms of one vibrational correlation function. This treatment unifies the fast and slow modulation approaches to vibrational dephasing and demonstrates how isotropic spontaneous Raman scattering studies and picosecond coherent probing experiments can be used in conjunction to study the inhomogeneous broadening of vibrational linewidths.

• Research Organization: Department of Chemistry and Materials and Molecular Research Division of Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 7026251
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 73:11; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640420* -- Fluid Physics-- Properties & Structure of Fluids-- (-1987)
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
FLUIDS
LINE BROADENING
LINE WIDTHS
LIQUIDS
MOLECULES
POLYATOMIC MOLECULES
RAMAN SPECTRA
SPECTRA
VIBRATIONAL STATES