Molecular Stability and the H₂ + D₂ → 2HD Four Center Exchange Reaction Surface

Citation

Wilson, Charles Woodrow, Jr. (1970) Molecular Stability and the H₂ + D₂ → 2HD Four Center Exchange Reaction Surface. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/PE87-HJ15. https://resolver.caltech.edu/CaltechTHESIS:11192009-140720848

Abstract

Partitions of the energy of the spin-coupling optimized GI wavefunctions of small systems are examined to isolate the factor responsible for chemical binding. One term, the contragradience energy, is found to dominate the binding energy in all cases. The magnitude of the contragradience energy is found to be insensitive to self-consistency effects; this property is used to extend the results to molecules too large for self-consistent calculation. Resonance, rotational barriers and the concept of a bond region are discussed in terms of the contragradience energy. Calculations of the reaction surface for the H_2 + D_2 → 2HD four-center exchange reaction are examined in terms of the contra-gradience energy.

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