Abinitiovibrational levels for HO2and vibrational splittings for hydrogen atom transfer

摘要

We calculate vibrational levels and wave functions for HO2using the recently reportedabinitiopotential energy points of Walch and Duchovic lsqb;J. Chem. Phys.94, 7068 (1991)rsqb; as fit by Dateo (unpublished). There is intramolecular hydrogen atom transfer when the hydrogen atom tunnels through a Thyphen;shaped saddle point separating the two equivalent equilibrium geometries, and correspondingly, the vibrational levels are split. We focus on vibrational levels and wave functions with significant splitting. The first three vibrational levels with splitting greater than 2 cmminus;1are (1,5,0), (0,7,1), and (0,8,0), wherev2is the Ondash;Ondash;H bend quantum number. We discuss the dynamics of hydrogen atom transfer; in particular, the Ondash;O distances at which hydrogen atom transfer is most probable for these vibrational levels.