S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering

Manthe U, Ellerbrock R (2016)
JOURNAL OF CHEMICAL PHYSICS 144(20): 204119.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
A new approach for the quantum-state resolved analysis of polyatomic reactions is introduced. Based on the singular value decomposition of the S-matrix, energy-dependent natural reaction channels and natural reaction probabilities are defined. It is shown that the natural reaction probabilities are equal to the eigenvalues of the reaction probability operator [U. Manthe and W. H. Miller, J. Chem. Phys. 99, 3411 (1993)]. Consequently, the natural reaction channels can be interpreted as uniquely defined pathways through the transition state of the reaction. The analysis can efficiently be combined with reactive scattering calculations based on the propagation of thermal flux eigenstates. In contrast to a decomposition based straightforwardly on thermal flux eigenstates, it does not depend on the choice of the dividing surface separating reactants from products. The new approach is illustrated studying a prototypical example, the H + CH4 -> H-2 + CH3 reaction. The natural reaction probabilities and the contributions of the different vibrational states of the methyl product to the natural reaction channels are calculated and discussed. The relation between the thermal flux eigenstates and the natural reaction channels is studied in detail. Published by AIP Publishing.
Erscheinungsjahr
Zeitschriftentitel
JOURNAL OF CHEMICAL PHYSICS
Band
144
Zeitschriftennummer
20
Artikelnummer
204119
ISSN
eISSN
PUB-ID

Zitieren

Manthe U, Ellerbrock R. S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering. JOURNAL OF CHEMICAL PHYSICS. 2016;144(20): 204119.
Manthe, U., & Ellerbrock, R. (2016). S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering. JOURNAL OF CHEMICAL PHYSICS, 144(20), 204119. doi:10.1063/1.4952478
Manthe, U., and Ellerbrock, R. (2016). S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering. JOURNAL OF CHEMICAL PHYSICS 144:204119.
Manthe, U., & Ellerbrock, R., 2016. S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering. JOURNAL OF CHEMICAL PHYSICS, 144(20): 204119.
U. Manthe and R. Ellerbrock, “S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering”, JOURNAL OF CHEMICAL PHYSICS, vol. 144, 2016, : 204119.
Manthe, U., Ellerbrock, R.: S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering. JOURNAL OF CHEMICAL PHYSICS. 144, : 204119 (2016).
Manthe, Uwe, and Ellerbrock, Roman. “S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering”. JOURNAL OF CHEMICAL PHYSICS 144.20 (2016): 204119.

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 27250291
PubMed | Europe PMC

Suchen in

Google Scholar