Abstract
Several formally exact expressions for quantum mechanical rate constants (i.e., bimolecular reactive cross sections suitably averaged and summed over initial and final states) are derived and their relation to one another analyzed. It is suggested that they may provide a useful means for calculating quantum mechanical rate constants accurately without having to solve the complete state-to-state quantum mechanical reactive scattering problem. Several ways are discussed for evaluating the quantum mechanical traces involved in these expressions, including a path integral evaluation of the Boltzmann operator/time propagator and a discrete basis set approximation. Both these methods are applied to a one-dimensional test problem (the Eckart barrier).
| Original language | English (US) |
|---|---|
| Pages (from-to) | 4889-4898 |
| Number of pages | 10 |
| Journal | The Journal of Chemical Physics |
| Volume | 79 |
| Issue number | 10 |
| State | Published - 1983 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
Cite this
Quantum mechanical rate constants for bimolecular reactions. / Miller, William H.; Schwartz, Steven D; Tromp, John W.
In: The Journal of Chemical Physics, Vol. 79, No. 10, 1983, p. 4889-4898.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Quantum mechanical rate constants for bimolecular reactions
AU - Miller, William H.
AU - Schwartz, Steven D
AU - Tromp, John W.
PY - 1983
Y1 - 1983
N2 - Several formally exact expressions for quantum mechanical rate constants (i.e., bimolecular reactive cross sections suitably averaged and summed over initial and final states) are derived and their relation to one another analyzed. It is suggested that they may provide a useful means for calculating quantum mechanical rate constants accurately without having to solve the complete state-to-state quantum mechanical reactive scattering problem. Several ways are discussed for evaluating the quantum mechanical traces involved in these expressions, including a path integral evaluation of the Boltzmann operator/time propagator and a discrete basis set approximation. Both these methods are applied to a one-dimensional test problem (the Eckart barrier).
AB - Several formally exact expressions for quantum mechanical rate constants (i.e., bimolecular reactive cross sections suitably averaged and summed over initial and final states) are derived and their relation to one another analyzed. It is suggested that they may provide a useful means for calculating quantum mechanical rate constants accurately without having to solve the complete state-to-state quantum mechanical reactive scattering problem. Several ways are discussed for evaluating the quantum mechanical traces involved in these expressions, including a path integral evaluation of the Boltzmann operator/time propagator and a discrete basis set approximation. Both these methods are applied to a one-dimensional test problem (the Eckart barrier).
UR - http://www.scopus.com/inward/record.url?scp=0343791207&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0343791207&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0343791207
VL - 79
SP - 4889
EP - 4898
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 10
ER -