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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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