Perturbation-wave packet studies of vibrational predissociation in collinear X--BC van der Waals complexes: HexxxI/sub 2/(B /sup 3/Pi)

Journal Article · Fri Oct 15 04:00:00 EDT 1982 · J. Chem. Phys.; (United States)

OSTI ID:6864408

Viswanathan, R; Raff, L M; Thompson, D L

A time-dependent wave packet method for the investigation of adiabatic vibrational predissociation (VP) of collinear X--BC systems is described. Discrete--discrete and discrete--continuum couplings are introduced into the initial wave function using a first-order perturbation procedure. The system wave packet is evolved in time by an explicit integration procedure and reaction probabilities P(t) as a function of time are computed by integrating the wave packet over the configuration space of the VP products. The VP rate coefficient is given directly by )-partial ln(1-P(t))/partialt). The method has been applied to the vibrational predissociation of He--I/sub 2/ (B /sup 3/Pi). Zero and first-order VP rate coefficients and decay half-widths have been computed as a function of initial I/sub 2/ vibrational state and X-atom mass for both pairwise harmonic and Morse potentials. Comparisons with previously reported distorted wave and quasiclassical trajectory calculations and with measured VP rates show all the methods to be of similar accuracy.

• Research Organization: Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078
• OSTI ID: 6864408
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 77:8; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640305* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Theory-- (-1987)
74 ATOMIC AND MOLECULAR PHYSICS
COMPLEXES
DISSOCIATION
ELEMENTS
ENERGY LEVELS
EXCITED STATES
FLUIDS
GASES
HALOGENS
HELIUM
IODINE
NONMETALS
PERTURBATION THEORY
PREDISSOCIATION
RARE GASES
VIBRATIONAL STATES
WAVE PACKETS