Computer simulation of the far infrared collision induced absorption spectra of gaseous CO2

Abstract

Far infrared collision induced absorption spectra of gaseous CO₂ were computed using molecular dynamics simulations. The quadrupole and hexadecapole multipolar induction, through the trace, and the anisotropy of the molecular polarizability were found to be insufficient to represent properly the dipole induction mechanism. For a detailed analysis of the induction process the spectra obtained were decomposed into components resulting from different terms of the induced dipole. Based on this decomposition, an additional overlap contribution for each term was proposed. When spectra were recomputed including such overlap, good agreement between experiment and simulation was achieved over the temperature range at which measurements exist (233-400K). The use of an anisotropic intermolecular potential was found to be of crucial importance for obtaining the right shape of the far wings of the spectra.