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Title: Molecular anions and the Born-Oppenheimer approximation

Abstract

The Born-Oppenheimer approximation is central to the understanding of many ages of chemistry. In this dissertation a description of molecular anions at the two extremes of the Born-Oppenheimer approximation is presented. Part one, Chapters 1, 2 and 3, covers the investigation of the breakdown of the Born-Oppenheimer approximation. Molecular anions with high vibrational and rotational energies, under the appropriate conditions, can eject electrons by a mechanism that couples the that couples the vibrational and rotational degrees of freedom to the electronic degrees of freedom. The vibration-rotation-induced electron detachment rates are calculated using a Fermi Golden rule approach in which the vibrationally rotationally hot anion is coupled to the colder neutral molecule plus an ejected electron. This requires the calculation of non-Born-Oppenheimer or nonadiabatic matrix elements. These matrix elements are calculated by both finite difference and analytical techniques and the method is applied to selected anion and neutral systems. In the second part of this dissertation, lightly solvated anions or clustered anion complexes are examined entirely within the limits of the Born-Oppenheimer approximation. The structure and relative energetics of the anion complexes, H{sup {minus}} (H{sub 2}) and H{sup {minus}} (H{sub 2}){sub 2}, using highly accurate state-of-the-art quantum chemical techniques, are describedmore » in Chapters 4 and 5 of this dissertation.« less

Authors:
Publication Date:
Research Org.:
Utah Univ., Salt Lake City, UT (USA)
OSTI Identifier:
6955703
Resource Type:
Miscellaneous
Resource Relation:
Other Information: Thesis (Ph. D)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; BORN-OPPENHEIMER APPROXIMATION; MOLECULAR IONS; ELECTRON DETACHMENT; ADIABATIC PROCESSES; ANIONS; DEGREES OF FREEDOM; ELECTRONS; HYDROGEN; MOLECULAR STRUCTURE; CHARGED PARTICLES; ELEMENTARY PARTICLES; ELEMENTS; FERMIONS; IONS; LEPTONS; NONMETALS; 640302* - Atomic, Molecular & Chemical Physics- Atomic & Molecular Properties & Theory

Citation Formats

Kendall, R A. Molecular anions and the Born-Oppenheimer approximation. United States: N. p., 1988. Web.
Kendall, R A. Molecular anions and the Born-Oppenheimer approximation. United States.
Kendall, R A. Fri . "Molecular anions and the Born-Oppenheimer approximation". United States.
@article{osti_6955703,
title = {Molecular anions and the Born-Oppenheimer approximation},
author = {Kendall, R A},
abstractNote = {The Born-Oppenheimer approximation is central to the understanding of many ages of chemistry. In this dissertation a description of molecular anions at the two extremes of the Born-Oppenheimer approximation is presented. Part one, Chapters 1, 2 and 3, covers the investigation of the breakdown of the Born-Oppenheimer approximation. Molecular anions with high vibrational and rotational energies, under the appropriate conditions, can eject electrons by a mechanism that couples the that couples the vibrational and rotational degrees of freedom to the electronic degrees of freedom. The vibration-rotation-induced electron detachment rates are calculated using a Fermi Golden rule approach in which the vibrationally rotationally hot anion is coupled to the colder neutral molecule plus an ejected electron. This requires the calculation of non-Born-Oppenheimer or nonadiabatic matrix elements. These matrix elements are calculated by both finite difference and analytical techniques and the method is applied to selected anion and neutral systems. In the second part of this dissertation, lightly solvated anions or clustered anion complexes are examined entirely within the limits of the Born-Oppenheimer approximation. The structure and relative energetics of the anion complexes, H{sup {minus}} (H{sub 2}) and H{sup {minus}} (H{sub 2}){sub 2}, using highly accurate state-of-the-art quantum chemical techniques, are described in Chapters 4 and 5 of this dissertation.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1988},
month = {1}
}

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