Intermolecular dynamics of substituted benzene and cyclohexane liquids, studied by femtosecond nonlinear-optical polarization spectroscopy

Yong Joon Chang, Edward W. Castner

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116 Scopus citations


Femtosecond time-resolved optical-heterodyne detected Roman-induced Kerr effect spectroscopy (OHD-RIKES) is shown to be a powerful and comprehensive tool for studying the intermolecular dynamics occurring in liquids. The observed dynamics include both the underdamped, or coherent inertial motions, and the longer time scale diffusive relaxation. The inertial dynamics include phonon-like intermolecular vibrations, intermolecular collisions, and librational caging motions. Data are presented and analyzed for a series of five liquids: cyclohexane, methylcyclohexane, toluene, benzyl alcohol, and benzonitrile, listed in order of increasing polarity. We explore the effects of aromaticity (e.g., methylcyclohexane vs. toluene), symmetry reduction (cyclohexane vs methylcyclohexane), and substitution effects (e.g., substituted benzene series) on the ultrafast intermolecular dynamics, for a group of molecular liquids of similar size and volume. We analyze the intermolecular dynamics in both the time and frequency domains by means of Fourier transformations. When Fourier-transformed into the frequency domain, the OHD-RIKES ultrafast transients of the intermolecular dynamics can be directly compared with the frequency domain spectra obtained from the far-infrared absorption and depolarized Raman techniques. This is done using the Gaussian librational caging model of Lynden-Bell and Steele, which results in a power-law scaling relation between dipole and polarizability time correlation functions. Last, we use a theoretical treatment of Maroncelli and co-workers to model for some of these liquids the solvation time-correlation function for the solvation of a charge-transfer excited-state chromophore based on the measured neat solvent dynamics.

Original languageEnglish (US)
Pages (from-to)3330-3343
Number of pages14
JournalJournal of physical chemistry
Issue number9
StatePublished - Feb 29 1996
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry


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