The equilibrium geometry of F2+in its ground electronic state. A simple example of the effects of symmetry breaking on an observable molecular property
作者:
Robert Murphy,
HenryF. Schaefer,
RossH. Nobes,
Leo Radom,
RussellM. Pitzer,
期刊:
International Reviews in Physical Chemistry
(Taylor Available online 1986)
卷期:
Volume 5,
issue 2-3
页码: 229-237
ISSN:0144-235X
年代: 1986
DOI:10.1080/01442358609353387
出版商: Taylor & Francis Group
数据来源: Taylor
摘要:
A wide variety of theoretical methods have been applied to a very simple but notoriously difficult problem, the calculation of the bond distance in F2+. All theoretical methods used the same basis set, the standard Huzinaga-Dunning double-zeta plus polarization (DZ + P) set, designated F (9s 5p 1d/4s 2p 1d). All methods which enforce inversion symmetry and go beyond second-order perturbation theory are qualitatively successful, giving bond distances within 005 Å of experiment. Methods not enforcing inversion symmetry are successful to within 003 Å if based on a restricted Hartree-Fock (RHF) starting point. When the wavefunction is not constrained to have inversion symmetry, methods based on an unrestricted Hartree-Fock (UHF) starting point are less satisfactory, yielding errors in the F2+bond distance ranging from 0-092 Å (full fourth-order perturbation theory, UMP4) to 0-850 Å (single-determinant UHF).
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