Halverson Thomas, Poirier Bill
Department of Chemistry and Biochemistry, and Department of Physics, Texas Tech University , P.O. Box 41061, Lubbock, Texas 79409-1061, United States.
J Phys Chem A. 2015 Dec 17;119(50):12417-33. doi: 10.1021/acs.jpca.5b07868. Epub 2015 Oct 12.
In this study, we compute all of the dynamically relevant vibrational quantum states of benzene, using an "exact" quantum dynamics (EQD) methodology. Benzene (C6H6), in addition to being a very large molecule for EQD (12 atoms, 30 vibrational modes), also has a very large number of vibrational states-around 10(6) in all, lying within 6500 cm(-1) of the ground state. The EQD methodology developed here uses a phase space picture to optimize the truncation of a harmonic oscillator basis-not only with respect to the molecular system of interest but also with respect to the targeted spectral range. By employing several such EQD calculations, targeted to different spectral ranges, a "hybridized" data set is constructed that provides the most accurate results everywhere. In particular, more than 500,000 states are converged to 15 cm(-1) or better.
