Collisional recombination reaction H+O-2+M->HO2+M: Quantum mechanical study using filter diagonalization

被引:52
作者
Mandelshtam, VA
Taylor, HS
Miller, WH
机构
[1] UNIV CALIF BERKELEY,DEPT CHEM,BERKELEY,CA 94720
[2] UNIV CALIF BERKELEY,LAWRENCE BERKELEY NATL LAB,DIV CHEM SCI,BERKELEY,CA 94720
关键词
D O I
10.1063/1.471903
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We report the results of calculations for the collisional recombination rate of the reaction H+O-2+M-->HO2+M. This study uses the recently developed quantum mechanical theory of recombination (within the strong collision approximation) based on the flux-flux correlation function analysis [J. Phys. Chem. 99, 12387 (1995)]. The quantum dynamics calculations are based on the new very efficient computational procedure of filter diagonalization [J. Chem. Phys. 103, 10074 (1995)]. This procedure allows one to obtain individual complex eigenenergies and eigenfunctions of a large non-Hermitian matrix representation of the Hamiltonian with an absorbing potential. The computed rates are compared to the Lindemann steady-state approximation result. The latter leads to an overestimation of the rate since it does not take into account the resonance interference effects. This becomes more critical at higher temperatures where many bread high energy overlapping resonances contribute to the rate. (C) 1996 American Institute of Physics.
引用
收藏
页码:496 / 503
页数:8
相关论文
共 43 条
[11]  
Glassman Irvin., 1977, COMBUSTION
[12]   RECURSION POLYNOMIAL EXPANSION OF THE GREENS-FUNCTION WITH ABSORBING BOUNDARY-CONDITIONS - CALCULATIONS OF RESONANCES OF HCO BY FILTER DIAGONALIZATION [J].
GROZDANOV, TP ;
MANDELSHTAM, VA ;
TAYLOR, HS .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (18) :7990-7995
[13]   RATE CONSTANTS FOR H+02+HE, H+02+N2, H+02+H20 FROM 298-K TO 639-K [J].
HSU, KJ ;
ANDERSON, SM ;
DURANT, JL ;
KAUFMAN, F .
JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (03) :1018-1021
[14]   POTENTIAL-ENERGY SURFACES FOR THE LOW-LYING (2)A'' AND (2)A' STATES OF HO2 - USE OF THE DIATOMICS IN MOLECULES MODEL TO FIT AB-INITIO DATA [J].
KENDRICK, B ;
PACK, RT .
JOURNAL OF CHEMICAL PHYSICS, 1995, 102 (05) :1994-2012
[15]   RECOMBINATION RESONANCES IN THERMAL H+O-2 SCATTERING [J].
KENDRICK, B ;
PACK, RT .
CHEMICAL PHYSICS LETTERS, 1995, 235 (3-4) :291-296
[16]  
KENDRICK B, UNPUB J CHEM PHYS
[17]   QUANTUM-MECHANICAL CALCULATION OF THE RATE-CONSTANT FOR THE REACTION H+O2-]OH+O [J].
LEFORESTIER, C ;
MILLER, WH .
JOURNAL OF CHEMICAL PHYSICS, 1994, 100 (01) :733-735
[18]   INFLUENCES OF CLOUD PHOTOCHEMICAL PROCESSES ON TROPOSPHERIC OZONE [J].
LELIEVELD, J ;
CRUTZEN, PJ .
NATURE, 1990, 343 (6255) :227-233
[19]   SPECTRAL PROJECTION APPROACH TO THE QUANTUM SCATTERING CALCULATIONS [J].
MANDELSHTAM, VA ;
TAYLOR, HS .
JOURNAL OF CHEMICAL PHYSICS, 1995, 102 (19) :7390-7399
[20]   BOUND-STATES AND RESONANCES OF THE HYDROPEROXYL RADICAL HO2 - AN ACCURATE QUANTUM-MECHANICAL CALCULATION USING FILTER DIAGONALIZATION [J].
MANDELSHTAM, VA ;
GROZDANOV, TP ;
TAYLOR, HS .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (23) :10074-10084