Polyatomic reaction dynamics

Technical Report · Mon Jul 01 04:00:00 EDT 1985

OSTI ID:5114378

Carrington, T

It is difficult to study the reaction dynamics of polyatomic systems. One of the principal problems is the calculation of the Born-Oppenheimer potential energy surface. In this thesis several useful approximations to the full potential energy surface are proposed and applied. The reaction path approximation to the potential is used to study the vinylidene-acetylene rearrangement. The reaction path approximation is not sufficient when one or more of the vibrational degrees of freedom is strongly coupled to the reaction coordinate. In this case it is necessary to expand the potential about a two dimensional surface (the reaction surface) rather than about a one dimensional path (the reaction path). Assuming this form for the potential the reaction surface Hamiltonian is derived. An even better approximation to the full potential energy surface is obtained by expanding the potential about the reaction surface in internal coordinates. A Hamiltonian which allows two internal coordinates to undergo arbitrarily large amplitude displacements is developed and applied to studying malonaldehyde. 57 refs., 5 figs., 1 tab.

• Research Organization: Lawrence Berkeley Lab., CA (USA)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5114378
• Report Number(s): LBL-20048; ON: DE86000609
• Country of Publication: United States
• Language: English

Related Subjects

640305* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Theory-- (-1987)
74 ATOMIC AND MOLECULAR PHYSICS
ACETYLENE
ALKYNES
BORN-OPPENHEIMER APPROXIMATION
CHEMICAL REACTION KINETICS
ENERGY LEVELS
EXCITED STATES
HAMILTONIANS
HYDROCARBONS
KINETICS
MATHEMATICAL OPERATORS
MOLECULES
ORGANIC COMPOUNDS
POLYATOMIC MOLECULES
QUANTUM OPERATORS
RADICALS
REACTION KINETICS
VIBRATIONAL STATES
VINYLIDENE RADICALS