C. Heidelbach et al., Molecular dynamics simulation of vibrational relaxation of highly excited molecules in fluids. II. Nonequilibrium simulation of azulene in CO2 and Xe, J CHEM PHYS, 110(11), 1999, pp. 5286-5299
Results of nonequilibrium molecular dynamics simulations of vibrational ene
rgy relaxation of azulene in carbon dioxide and xenon at low and high press
ure are presented and analyzed. Simulated relaxation times are in good agre
ement with experimental data for all systems considered. The contribution o
f vibration-rotation coupling to vibrational energy relaxation is shown to
be negligible. A normal mode analysis of solute-to-solvent energy flux reve
als an important role of high-frequency modes in the process of vibrational
energy relaxation. Under all thermodynamic conditions considered they take
part in solvent-assisted intramolecular energy redistribution and, moreove
r, at high pressure they considerably contribute to azulene-to-carbon dioxi
de energy flux. Solvent-assisted (or collision-induced) intermode energy ex
change seems to be the main channel, ensuring fast intramolecular energy re
distribution. For isolated azulene intramolecular energy redistribution is
characterized by time scales from several to hundreds of ps and even longer
, depending on initial excitation. The major part of solute vibrational ene
rgy is transferred to the solvent via solute out-of-plane vibrational modes
. In-plane vibrational modes are of minor importance in this process. Howev
er, their contribution grows with solvent density. The distribution of ener
gy fluxes via azulene normal modes strongly depends on thermodynamic condit
ions. The contribution of hydrogen atoms to the overall solute-to-solvent e
nergy flux is approximately two to three times higher than of carbon atoms
depending on the system and thermodynamic conditions as well. Carbon atoms
transfer energy only in the direction perpendicular to the molecular plane
of azulene, whereas hydrogen atoms show more isotropic behavior, especially
at high pressure. (C) 1999 American Institute of Physics. [S0021-9606(99)5
1311-1].