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A Quantum-Mechanical Discussion of the Bifluoride Ion


Karplus, Martin (1954) A Quantum-Mechanical Discussion of the Bifluoride Ion. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/EY65-WG09.


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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.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:(Chemistry and Biology)
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Minor Option:Biology
Awards:The Nobel Prize in Chemistry, 2013.
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Pauling, Linus
Group:Nobel Prize
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1954
Additional Information:The Nobel Prize in Chemistry 2013 was awarded jointly to Martin Karplus, Michael Levitt and Arieh Warshel "for the development of multiscale models for complex chemical systems."
Record Number:CaltechETD:etd-01072004-094608
Persistent URL:
Related URLs:
URLURL TypeDescription Prize announcement (Chemistry, 2013)
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44
Deposited By: Imported from ETD-db
Deposited On:08 Jan 2004
Last Modified:08 Jun 2023 23:53

Thesis Files

PDF (Karplus_m_1954.pdf) - Final Version
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