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Electron correlation and relativistic effects in xenon tetrafluoride
Author(s) -
Styszynski Jacek,
Malli Gulzari L.
Publication year - 1995
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560550303
Subject(s) - electronic correlation , atomic physics , relativistic quantum chemistry , chemistry , electron , basis set , bond dissociation energy , ab initio , hartree–fock method , physics , ab initio quantum chemistry methods , dissociation (chemistry) , molecule , quantum mechanics
Ab initio all ‐ electron fully relativistic Dirac–Fock self‐consistent field and Dirac–Fock–Breit calculations are reported for the XeF 4 molecule at various internuclear distances assuming the experimental D 4 h geometry with our recently developed relativistic universal Gaussian basis set. The nonrelativistic limit Hartree–Fock calculations were also performed for XeF 4 at various internuclear distances. The calculated relativistic correction to the total energy of molecule at the Dirac–Fock level is ∼ −5856 eV, whereas the magnetic part of the Breit correction to the electron‐electron interaction is calculated as ∼ 177 eV. The electron correlation effects were included in the nonrelativistic Hartree–Fock calculations using the second‐order Møller‐Plesset ( MP 2) theory, and the calculated correlation energy for XeF 4 is −71 eV. The basis‐set superposition error ( BSSE ) was estimated by using the counterpoise method for Xe and F. The inclusion of both the relativistic and electron correlation effects in the calculated total energies of F, Xe, and XeF 4 predicts the Xe—F bond length and dissociation energy of XeF 4 as 1.952 Å and 5.59 eV, respectively, which are in excellent agreement with the experimental values of 1.953 Å and 5.69 eV, respectively, for XeF 4 . The contribution of the electron correlation and relativistic effects to the dissociation energy of XeF 4 is 8.11 and 0.05 eV, respectively. The Breit interaction, however, contributes only 0.02 eV to the dissociation energy of XeF 4 . Electron correlation is most significant for the prediction of an accurate value of dissociation energy, whereas relativistic effects are very important for the prediction of spin‐orbital splitting as well as the energies of the orbitals, especially the inner orbitals of XeF 4 . © 1995 John Wiley & Sons, Inc.