Theoretical study of indirect photodissociation: Electronic structure and product rovibrational distributions of C/sub 2/N/sub 2/(C-tilde /sup 1/PI/sub u/)
Polyatomic indirect photodissociation is treated as a quantum transition between quasidiscrete and dissociative (photofragment) states within a diabatic representation of the electronic Hamiltonian following a formalism developed by Kresin and Lester (KL). Relative product energy distributions are obtained from the evaluation of a multidimensional Franck-Condon overlap integral. The KL adiabatic method is followed to describe the nuclear dynamics of the dissociative state. The theory is applied to single-photon dissociation of C/sub 2/N/sub 2/(C-tilde /sup 1/PI/sub u/) at 164, 158.7, and 153.6 nm to form CN(X /sup 2/..sigma../sup +/) + CN(A /sup 2/PI). Ab initio multiconfiguration Hartree-Fock (MCHF) excited state calculations are carried out to provide essential potential energy surface properties for the heavy-particle dynamics treatment. Product vibrational distributions are obtained in a collinear model and theoretical predictions are found to be in good agreement with recent experiments. An extension of the theory to 3-dimensions is described. Product rovibrational distributions and rotational temperatures are reported which take into account bending-vibrational modes and rotations employing only the adiabatic sudden limit of the general formalism of KL. 106 refs., 15 figs., 25 tabs.
- Research Organization:
- Lawrence Berkeley Lab., CA (USA)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5889871
- Report Number(s):
- LBL-23944; ON: DE88000466
- Resource Relation:
- Other Information: Thesis (Ph.D.). Portions of this document are illegible in microfiche products
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CYANOGEN
ELECTRONIC STRUCTURE
PHOTOLYSIS
PREDISSOCIATION
DISSOCIATION
ADIABATIC APPROXIMATION
ANGULAR MOMENTUM
BOND LENGTHS
CHEMICAL BONDS
CONFIGURATION
DISSOCIATION ENERGY
EXCITED STATES
FRANCK-CONDON PRINCIPLE
GROUND STATES
HAMILTONIANS
HARMONICS
HARTREE-FOCK METHOD
MOLECULES
OSCILLATION MODES
QUANTUM MECHANICS
ROTATIONAL STATES
SYMMETRY
VIBRATIONAL STATES
CHEMICAL REACTIONS
DECOMPOSITION
DIMENSIONS
ENERGY
ENERGY LEVELS
LENGTH
MATHEMATICAL OPERATORS
MECHANICS
OSCILLATIONS
PHOTOCHEMICAL REACTIONS
QUANTUM OPERATORS
400500* - Photochemistry