Citation
Hunt, William James (1972) Electronic wavefunctions for small molecules. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:11122009074130644
Abstract
PART I. A simple variationallybased method for calculating electronic wavefunctions of excited states, the improved virtual orbital (IVO) method, is developed in this work. Calculations are presented for H_2O, O_2, CO, and N_2. While the IVO method gives limited accuracy in the treatment of valence excited states, the description of Rydberg states is very useful. For O_2 the theoretical prediction of 8.70 eV (v' = 2) for the transition from the ^3Σ^_g ground state to the ^3π_g (1π_g → 3sσ_g) Rydberg state facilitated discovery of this transition in electron impact spectra at 8.65 eV (v' = 2). PART II. The N, T, and V states of ethylene have been studied with the HartreeFoci (HF) and configuration interaction (CI) techniques as a function of CC bond distance and the twist angle between methylene groups. The calculated rotational barrier for the N state is 67.2 Kcal/mole, in good agreement with the experimentally derived activation energy of 65 Kcal/mole for cistrans isomerization of 1,2dideutero ethylene. The maximum in the N state curve lies 1.4 Kcal/mole above the minimum of the triplet state (T) curve. Both HF end CI calculations show that the V state of planar ethylene has a more extended charge distribution than the T state. This charge distribution contracts as the methylene groups are twisted from the planar geometry. Correlation terms included in the CI calculations contract the charge distribution considerably from its HF size. A modified FranckCondon Principle for internal rotation suggests that the maximum absorption observed experimentally does not correspond to vertical excitation for the N → V transition. PART III. A Generalized Valence Bond method combining the computational tractability of the usual MOSCF approach with the conceptual advantages of a valence bond picture is proposed. The GVB method has been applied to calculation of potential curves for CH_2 in the ^3B_1, ^1A_1, and ^1B_1 states. These calculations predict that the ^3B_1 curve may cross the ^1A_1 curve near the minimum for the^1A_1 state. A study of the ring opening of cycloprooane predicts a barrier height of 61 Kcal/mole for cistrans isomerization, in good agreement with the experimentally determined activation energy of 65 Kcal/mole for 1,2 dideutero cyclopropene. An investigation of diatomic hydrides and fluorides in the GVB picture gives a consistent view of the energy levels and oneelectron energies of these molecules.
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:  20 September 1971 
Record Number:  CaltechTHESIS:11122009074130644 
Persistent URL:  http://resolver.caltech.edu/CaltechTHESIS:11122009074130644 
Default Usage Policy:  No commercial reproduction, distribution, display or performance rights in this work are provided. 
ID Code:  5366 
Collection:  CaltechTHESIS 
Deposited By:  Tony Diaz 
Deposited On:  17 Nov 2009 22:14 
Last Modified:  26 Dec 2012 03:18 
Thesis Files

PDF
 Final Version
See Usage Policy. 5Mb 
Repository Staff Only: item control page