Efficient polynomial expansion of the scattering Green's function: Application to the D+H[sub 2]([ital v]=1) rate constant

Journal Article · Sat Jan 15 04:00:00 EST 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.466642· OSTI ID:5445298

Auerbach, S M; Miller, W H ^[1]

---

1. Department of Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States)

We apply the absorbing boundary condition (ABC) discrete variable representation (DVR) theory of quantum reactive scattering to the initial state selected D+H[sub 2]([ital v]=1, [ital j])[r arrow]DH+H reaction. The ABC-DVR Green's function is efficiently computed by a Newton polynomial expansion. We compute accurate reaction probabilities for the total energies and angular momenta required to obtain the thermal rate constants [ital k][sub [ital v]=1, [ital j]]([ital T]). At [ital T]=310 K, a thermal average over [ital j]=(0,1,2,3) is performed to yield the final result [ital k][sub [ital v]=1](310 K)=1.87[times]10[sup [minus]13] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1], in [ital quantitative] agreement with the most recent experimental value (1.9[plus minus]0.2)[times]10[sup [minus]13] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1]. The [ital J]-shifting approximation using accurate [ital J]=0 reaction probabilities is tested against the exact results. It reliably predicts [ital k][sub [ital v]=1]([ital T]) for temperatures up to 700 K, but individual ([ital v]=1, [ital j]) selected rate constants are in error by as much as 41%.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5445298
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 100:2; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
BOUNDARY CONDITIONS
CHEMICAL REACTIONS
COLLISIONS
DEUTERIDES
DEUTERIUM
DEUTERIUM COMPOUNDS
ELEMENTS
ENERGY LEVELS
EXCITED STATES
FUNCTIONS
GREEN FUNCTION
HEAT RATE
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN DEUTERIDE
HYDROGEN ISOTOPES
ISOTOPES
LIGHT NUCLEI
MECHANICS
MOLECULE COLLISIONS
NONMETALS
NUCLEI
ODD-ODD NUCLEI
POLYNOMIALS
PROBABILITY
QUANTUM MECHANICS
STABLE ISOTOPES
TEMPERATURE RANGE
TEMPERATURE RANGE 0273-0400 K
USES
VIBRATIONAL STATES