NON-RESONANT RAMAN SPECTRA OF THE METHYL RADICAL 12CH3 SIMULATED IN VARIATIONAL CALCULATIONS

Abstract

We report first-principles variational simulation of the non-resonant Raman spectrum for methyl radical ($^{12}$CH$_3$) in the electronic ground state. Calculations are based on a high level \emph{ab initio} potential energy and polarizability tensor surfaces of CH$_3$ and employ accurate variational treatment of the ro-vibrational dynamics implemented in the general code TROVE [S. N. Yurchenko, W. Thiel, and P. Jensen, {\it J. Mol. Spectrosc.} {\bf 245}, 126--140 (2007); A. Yachmenev and S. N. Yurchenko, {\it J. Chem. Phys.} {\bf 143}, 014105 (2015)]. We extend the capabilities of TROVE towards simulations of the Raman spectra, which can in be applied to arbitrary molecule of moderate size. The simulations for CH$_3$ are found to be in a good agreement with the available experimental data.