Non-Resonant Raman Spectra of the Methyl Radical 12ch3 Simulated in Variational Calculations

Abstract

a b s t r a c tWe report first-principles variational simulation of the non-resonant Raman spectrum for the methyl radical ( 12 CH 3 ) in the electronic ground state. Calculations are based on a high level ab initio potential energy and dipole moment surfaces of CH 3 and employ the accurate variational treatment of the ro-vibrational dynamics implemented in the general code TROVE [S. N. Yurchenko, W. Thiel, and P. Jensen, J. Mol. Spectrosc. 245, 126-140 (2007); A. Yachmenev and S. N. Yurchenko, J. Chem. Phys. 143, 014105 (2015)]. TROVE can be applied to arbitrary molecules of moderate size and we extend here its capabilities towards simulations of Raman spectra. The simulations for CH 3 are found to be in a good agreement with the available experimental data.