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Understanding relativistic effects of chemical bonding
Author(s) -
Schwarz W. H. E.,
Rutkowski A.,
Wang S. G.
Publication year - 1996
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/(sici)1097-461x(1996)57:4<641::aid-qua11>3.0.co;2-3
Subject(s) - relativistic quantum chemistry , virial theorem , physics , pauli exclusion principle , perturbation theory (quantum mechanics) , kinetic energy , perturbation (astronomy) , degenerate energy levels , elliptic flow , ion , quantum mechanics , heavy ion , galaxy
Abstract To elucidate the physical origin of relativistic changes of molecular properties, exact theorems, perturbation theory, and Hartree‐Fock‐Slater‐Pauli calculations are exploited. The relativistic molecular virial theorem offers insight into the relativistic and nonrelativistic, kinetic, and potential energy contributions to the bond energy. In general, there exist two contributions to the relativistic correction of a molecular property: the relativistic change at the nonrelativistic equilibrium geometry and the change of the nonrelativistic property due to the relativistic change of the equilibrium geometry. Sometimes the first and sometimes the second contribution is the dominant one. Accurate numerical results for H + 2 ‐like systems are obtained using direct relativistic double perturbation theory. In some cases, near‐degenerate perturbation theory is mandatory. Relativistic changes of chemical bond energies are often proportional to the density change in the K‐shell when the bond is formed. Relativistic corrections to many properties (and also to the 1s 2 ‐correlation energy) are often proportional to Z 2 α 2 . © 1996 John Wiley & Sons, Inc.