THE IMPORTANCE OF RELATIVISTIC EFFECTS FOR CALCULATING SPECTROSCOPIC CONSTANTS FOR MOLECULES CONTAINING VERY HEAVY ATOMS

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Title: THE IMPORTANCE OF RELATIVISTIC EFFECTS FOR CALCULATING SPECTROSCOPIC CONSTANTS FOR MOLECULES CONTAINING VERY HEAVY ATOMS
Creators: Wadt, W. R.; Hay, P. Jeffrey; Kahn, Luis R.
Issue Date: 1978
Publisher: Ohio State University
Abstract: Ab initio multi-configuration SCF and configuration interaction calculations are reported on the ground states of AuH and AuCl using both $relativlstic^{1}$ and $nonrelativistic^{2}$ effective core potentials for gold. Calculations on the gold atom reveal that nonrelativistic wavefunctions lead to large errors (1-2 eV) in the binding energies and sizes of the valence 6s and 5d orbitals. These errors carry over to the molecular system so that nonrelativistic calculations can lead to 0.2-0.5 {\AA} errors in $R_{e}$ and 0.5 eV errors in $D_{e}$. Similarly large errors are encountered in other properties such as dipole moments. The origin of these errors is readily understood and will be discussed.
Description: $^{1}$ L. R. Kahn, P. J. Hay and R. D. Cowan, J, Chem. Phys., in press. $^{2}$ L. R. Kahn, P. Baybutt and D. G. Truhlar, J. Chem. Phys. 65, 3826(1976). ""
Author Institution: Los Alamos Scientific Laboratory; Battelle Columbus Laboratories
URI: http://hdl.handle.net/1811/10553
Other Identifiers: 1978-RH-03
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