A new (cartesian) reaction path model for dynamics in polyatomic systems, with application to H-atom transfer in malonaldehyde
A new kind of reaction path model for describing reactions in polyatomic molecular systems is presented, one which is based on the cartesian coordinates of the atoms. Not only does this lead to a simpler treatment of the interaction between the )openreverse arrowquotes)system)closereverse arrowquotes) (i.e., the reaction coordinate) and the )openreverse arrowquotes)bath)closereverse arrowquotes) (the other degrees of freedom) than earlier reaction path models based on the (curvilinear) steepest reaction path, but in many cases it also provides a more natural description of the dynamics. The resulting Hamiltonian has the standard form of a cartesian )openreverse arrowquotes)system)closereverse arrowquotes) linearly coupled to a harmonic )openreverse arrowquotes)bath)closereverse arrowquotes), the dynamics of which is treated in this paper by the basis set method of Makri and Miller. Application to a model of H-atom transfer in malonaldehyde shows that the overall approach - both the cartesian reaction path model and the basis set method treatment of the dynsmics - is quite successful. 20 refs., 1 tab.
- Research Organization:
- California Univ., Berkeley (USA). Dept. of Chemistry; Lawrence Berkeley Lab., CA (USA)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5355515
- Report Number(s):
- LBL-24412; CONF-871265-1; ON: DE88006350
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
99 GENERAL AND MISCELLANEOUS
990230 -- Mathematics & Mathematical Models-- (1987-1989)
ALDEHYDES
ATOMS
CARBOXYLIC ACIDS
CARTESIAN COORDINATES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COORDINATES
DICARBOXYLIC ACIDS
DYNAMICS
HAMILTONIANS
HYDROGEN TRANSFER
KINETICS
MALONIC ACID
MATHEMATICAL MODELS
MATHEMATICAL OPERATORS
MECHANICS
MOLECULES
ORGANIC ACIDS
ORGANIC COMPOUNDS
POLYATOMIC MOLECULES
QUANTUM OPERATORS
REACTION KINETICS