Time independent quantum theory of electron transfer collisions using a nonorthogonal basis and R-matrix propagation

T. G. Schmalz, Ellen Stechel, J. C. Light

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

We briefly review the difficulties associated with the traditional adiabatic quantum treatment of low energy charge transfer collisions between atoms and suggest that the charge transfer problem can be most conveniently treated by using atomic-centered basis functions and expressing the Hamiltonian simultaneously with respect to two separate atomic origins. As a result, we must solve the quantum nuclear equations of motion in a nonorthogonal basis. We demonstrate that this may be efficiently done by building the R -matrix propagator in this basis. Flux is automatically conserved even though the R matrix is built up from a series of nonunitary transformations. A simple model problem designed to represent the radial coupling in the reaction Li ++ Na→Li+ Na+ is solved to illustrate the technique.

Original languageEnglish
Pages (from-to)5660-5671
Number of pages12
JournalJournal of Chemical Physics
Volume70
Issue number12
Publication statusPublished - 1979

Fingerprint

Quantum theory
quantum theory
Charge transfer
electron transfer
charge transfer
Hamiltonians
collisions
propagation
Electrons
Equations of motion
equations of motion
Fluxes
Atoms
atoms
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Time independent quantum theory of electron transfer collisions using a nonorthogonal basis and R-matrix propagation. / Schmalz, T. G.; Stechel, Ellen; Light, J. C.

In: Journal of Chemical Physics, Vol. 70, No. 12, 1979, p. 5660-5671.

Research output: Contribution to journalArticle

@article{d9c346baf7734c30b2238536fd2b083e,
title = "Time independent quantum theory of electron transfer collisions using a nonorthogonal basis and R-matrix propagation",
abstract = "We briefly review the difficulties associated with the traditional adiabatic quantum treatment of low energy charge transfer collisions between atoms and suggest that the charge transfer problem can be most conveniently treated by using atomic-centered basis functions and expressing the Hamiltonian simultaneously with respect to two separate atomic origins. As a result, we must solve the quantum nuclear equations of motion in a nonorthogonal basis. We demonstrate that this may be efficiently done by building the R -matrix propagator in this basis. Flux is automatically conserved even though the R matrix is built up from a series of nonunitary transformations. A simple model problem designed to represent the radial coupling in the reaction Li ++ Na→Li+ Na+ is solved to illustrate the technique.",
author = "Schmalz, {T. G.} and Ellen Stechel and Light, {J. C.}",
year = "1979",
language = "English",
volume = "70",
pages = "5660--5671",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "12",

}

TY - JOUR

T1 - Time independent quantum theory of electron transfer collisions using a nonorthogonal basis and R-matrix propagation

AU - Schmalz, T. G.

AU - Stechel, Ellen

AU - Light, J. C.

PY - 1979

Y1 - 1979

N2 - We briefly review the difficulties associated with the traditional adiabatic quantum treatment of low energy charge transfer collisions between atoms and suggest that the charge transfer problem can be most conveniently treated by using atomic-centered basis functions and expressing the Hamiltonian simultaneously with respect to two separate atomic origins. As a result, we must solve the quantum nuclear equations of motion in a nonorthogonal basis. We demonstrate that this may be efficiently done by building the R -matrix propagator in this basis. Flux is automatically conserved even though the R matrix is built up from a series of nonunitary transformations. A simple model problem designed to represent the radial coupling in the reaction Li ++ Na→Li+ Na+ is solved to illustrate the technique.

AB - We briefly review the difficulties associated with the traditional adiabatic quantum treatment of low energy charge transfer collisions between atoms and suggest that the charge transfer problem can be most conveniently treated by using atomic-centered basis functions and expressing the Hamiltonian simultaneously with respect to two separate atomic origins. As a result, we must solve the quantum nuclear equations of motion in a nonorthogonal basis. We demonstrate that this may be efficiently done by building the R -matrix propagator in this basis. Flux is automatically conserved even though the R matrix is built up from a series of nonunitary transformations. A simple model problem designed to represent the radial coupling in the reaction Li ++ Na→Li+ Na+ is solved to illustrate the technique.

UR - http://www.scopus.com/inward/record.url?scp=36749112924&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=36749112924&partnerID=8YFLogxK

M3 - Article

VL - 70

SP - 5660

EP - 5671

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 12

ER -