A Quantum-Mechanical Discussion of the Bifluoride Ion

Author: Karplus, Martin

Year: 1954

Degree: Dissertation (Ph.D.)

Advisor: Pauling, Linus

Committee Member: Unknown, Unknown

Option: Chemistry; Biology

DOI: 10.7907/EY65-WG09

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document.

The variation method for obtaining approximate solutions to the Schrodinger equation is examined. It is demonstrated that one-electron orbitals can to employed in the construction of a convergent variation function. As special cases of the one-electron approach, the valence bond and molecular orbital methods are discused and compared.

Variation functions containing only a few terms are known to lead to incorrect results. The reasons for this failure are discussed. A semi-theoretical apnroach, which corrects some of the failings, is developed and tested on HF. Results in good agreement with experimental determinations of the energy and dipole moment are obtained. Application of the method to FHF⁻ leads to a value of 36.5 kcal for the energy of the reaction

F⁻ + HF → FHF⁻

Calculation of the FHF⁻ wave function shows that the completely ionic structure (F⁻ H⁺ F⁻) makes the largest contribution.

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