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The Equivalent Bond Orbital Model Revisited: I. Orbitals, Orbital Energies and PE Spectra of Saturated Hydrocarbons

Evi Honegger ; Physikalisch-Chemisches Institut, Universitat Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland
Zhong-zhi Yang ; Physikalisch-Chemisches Institut, Universitat Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland
Edgar Heilbronner ; Physikalisch-Chemisches Institut, Universitat Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland

Sažetak

The EBO model, originally proposed by Lennard-Jones and
Hall, many years ago, is reexamined using localized orbitals (LMO)
stemming from SCF ab initio calculations. It is found that only a·
limited set of matrix elements is needed to build a Fock matrix
F, (in localized basis) the diagonalization of which yields orbital
energies of sufficient precision for use in the assignment of photoelectron
spectra within Koopmans e1pproximation. The model so
obtained can be easily parametrized with respect to a given calibration
set, if the relative size of the off-diagonal elements suggested
by the ab initio calculation is conserved. It is argued that such
EBO models, which are essentially of Hiickel-type, Cl'!'e necessary
for the qualitative or semi-quantitative rationalization of experimental
and theoretical data (from more sophisticated calculations).
Some of the more important limitations of LMO-based EBO
models ctre discussed.

Ključne riječi

Hrčak ID:

194068

URI

https://hrcak.srce.hr/194068

Datum izdavanja:

14.1.1985.

Posjeta: 491 *