title: A novel Gaussian Binning (1GB) analysis of vibrational state distributions in highly excited H2O from reactive quenching of OH∗ by H2.
abstract: As shown in experiments by Lester and co-workers [J. Chem. Phys. 110, 11117 (1999)], the reactive quenching of OH∗ by H2 produces highly excited H2O. Previous limited analysis of quasiclassical trajectory calculations using standard Histogram Binning (HB) was reported [B. Fu, E. Kamarchik, and J. M. Bowman, J. Chem. Phys. 133, 164306 (2010)]. Here, we examine the quantized internal state distributions of H2O in more detail, using two versions of Gaussian Binning (denoted 1GB). In addition to the standard version of 1GB, which relies on the harmonic energies of the states (1GB-H), we propose a new and more accurate technique based on exact quantum vibrational energies (1GB-EQ). Data from about 42,000 trajectories from previous calculations that give excited water molecules are used in the two versions of 1GB as well as HB. For the vibrationally hot molecules considered in this study, the classical internal energy distribution serves as a benchmark to estimate the accuracy of the different binning methods analyzed. The 1GB discretization methods, especially the one using exact quantum energies, reconstruct the classical distribution much more accurately than HB and also the original, more elaborate Gaussian Binning method. Detailed quantum state distributions are presented for pure overtone excitations as well as several antisymmetric stretch distributions. The latter are focused on because the antisymmetric stretch has the largest emission oscillator strength of the three water modes.
authors.affiliation: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA. riccardo.conte@emory.edu
authors.forename: Riccardo
authors.initials: R
authors.lastname: Conte
authors.forename: Bina
authors.initials: B
authors.lastname: Fu
authors.forename: Eugene
authors.initials: E
authors.lastname: Kamarchik
authors.forename: Joel M
authors.initials: JM
authors.lastname: Bowman