Citation
Bowman, Joel Mark (1975) Theoretical Studies of Electronically Adiabatic and NonAdiabatic Chemical Reaction Dynamics. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/6F8NZE84. https://resolver.caltech.edu/CaltechTHESIS:02142012112644269
Abstract
Part I presents several sets of comparisons of semiclassical, quasiclassical and exact quantum reactive scattering calculations for collinear chemical reactions. The possibility of modifying the standard quasiclassical method according to a quantum criterion is investigated. The systems studied are H + H_2, F + H_2, and F + D_2. In addition, a theoretical investigation of the semiclassical S matrix is made.
Details of a quasiclassical current density analysis of the H + H_2 reaction are presented and a comparison with exact quantum results is made.
A direct test of two versions of the vibrationally adiabatic theory of chemical reactions is made in Part II for the H + H_2 reaction. The adiabaticity of the symmetric stretch motion of the H_3 transition state is focussed upon. In addition, a determination of the completeness of adiabatic basis sets for scattering calculations is made.
The theory of electronically nonadiabatic chemical reactions is presented in Part III. Quantum calculations of the collinear H^+ + H_2 → H_2 + H^+ reaction are described. A model and a realistic potential energy surface are employed in these calculations.
A fictitious electronically nonadiabatic H + H_2 collinear chemical reaction is treated quantum mechanically. Two potential energy surfaces and a coupling surface are developed for this purpose.
The reaction Ba(^1S) + ON_2(X^1Σ) → BaO(X^1Σ) + N_2(X^1Σ^+_g), BaO(a^3II) + N_2(X^1Σ^+_g) is studied quantum mechanically. The singlet and triplet potential energy surfaces are devised as is a spinorbit coupling surface. Electronically adiabatic and nonadiabatic transition probabilities are calculated as a function of the initial translational energy of the reagents.
Item Type:  Thesis (Dissertation (Ph.D.)) 

Subject Keywords:  (Chemistry) 
Degree Grantor:  California Institute of Technology 
Division:  Chemistry and Chemical Engineering 
Major Option:  Chemistry 
Thesis Availability:  Public (worldwide access) 
Research Advisor(s): 

Thesis Committee: 

Defense Date:  18 September 1974 
Record Number:  CaltechTHESIS:02142012112644269 
Persistent URL:  https://resolver.caltech.edu/CaltechTHESIS:02142012112644269 
DOI:  10.7907/6F8NZE84 
Default Usage Policy:  No commercial reproduction, distribution, display or performance rights in this work are provided. 
ID Code:  6820 
Collection:  CaltechTHESIS 
Deposited By:  Benjamin Perez 
Deposited On:  14 Feb 2012 21:19 
Last Modified:  02 Aug 2024 19:58 
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