Molecular anions and the Born-Oppenheimer approximation

Thesis/Dissertation · Fri Jan 01 04:00:00 EST 1988

OSTI ID:6955703

Kendall, R A

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.

• Research Organization: Utah Univ., Salt Lake City, UT (USA)
• OSTI ID: 6955703
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ADIABATIC PROCESSES
ANIONS
BORN-OPPENHEIMER APPROXIMATION
CHARGED PARTICLES
DEGREES OF FREEDOM
ELECTRON DETACHMENT
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
FERMIONS
HYDROGEN
IONS
LEPTONS
MOLECULAR IONS
MOLECULAR STRUCTURE
NONMETALS