New approach to quantum mechanical transition-state theory

Journal Article · Thu Jul 31 04:00:00 EDT 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100407a006· OSTI ID:5459605

Tromp, J W; Miller, W H

Classical transition-state theory is based on the direct, short-time (actually, zero time) classical dynamics through a dividing surface that separates reactants and products. This paper defines a new quantum mechanical version of transition-state theory by using the reactive flux correlation function of Miller, Schwartz, and Tromp (J. Chem. Phys. 1983, 79, 4889) to identify the short-time quantum dynamics through the dividing surface. It is seen that short time quantum mechanically is not zero time, as it is classically, but rather a time of order Planck's constant..beta... This new quantum version of transition-state theory is also seen to have some of the variational character of the classical case. Finally, it is shown how the reactive flux correlation function of Miller, Schwartz, and Tromp can be generalized by choosing various forms of the projector onto reactants, and this is seen to have important consequences for the accuracy of this new quantum transition-state theory.

• Research Organization: Univ. of California, Berkeley
• OSTI ID: 5459605
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:16; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTION KINETICS
DATA
INFORMATION
KINETICS
MATHEMATICAL MODELS
MECHANICS
NUMERICAL DATA
POTENTIALS
QUANTUM MECHANICS
REACTION KINETICS
THEORETICAL DATA
THERMODYNAMICS