Classical, non-linear, internal dynamics of large, isolated, vibrationally excited molecules

Abstract

This work reports numerical experiments intended to clarify the internal equilibration process in large molecules, following vibrational excitation. A model of amorphous and oxygenated hydrocarbon macromolecule (about 500 atoms)--simulating interstellar dust-- is built up by means of a chemical simulation code. Its structure is optimized, and its normal modes determined. About 4.5 eV of potential energy is then deposited locally by perturbing one of the C-H peripheral bonds, thus simulating the capture of a free H atom by a dangling C bond. The ensuing relaxation of the system is followed for up to 300 ps, using a molecular mechanics code. When steady state is reached, spectra and time correlation functions of kinetic energy and bond length fluctuations indicate that most normal modes have been activated, but the motion remains quasi-periodic or regular. By contrast, when the molecule is violently excited or embedded in a thermal bath (modelled by Langevin dynamics), the same markers clearly depict chaotic motions. Thus it appears that even such a large system of oscillators is unable to provide the equivalent of a thermal bath to any one of these, unless there are strong resonances between some of them. In general, therefore, an energy of a few eV's deposited in an isolated molecule will not be immediately thermalized. This conclusion is of consequence for the interpretation of astronomical UIB spectra. Key Words:IS dust--UIBs--Excitation, relaxation processes.