Premium
Ionization potentials and electron affinities of Cu, Ag, and Au: Electron correlation and relativistic effects
Author(s) -
Neogrády Pavel,
Kellö Vladimir,
Urban Miroslav,
Sadlej Andrzej J.
Publication year - 1997
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(1997)63:2<557::aid-qua25>3.0.co;2-3
Subject(s) - electron , ionization , affinities , electronic correlation , atomic physics , relativistic quantum chemistry , ionization energy , electron affinity (data page) , electron ionization , chemistry , physics , ion , nuclear physics , quantum mechanics , molecule , stereochemistry
The electron correlation and relativistic effects on ionization potentials and electron affinities of Cu, Ag, and Au are investigated in the framework of the coupled cluster method and different 1‐component approximations to the relativistic Dirac‐Coulomb Hamiltonian. The first‐order perturbation approach based on the massvelocity and Darwin terms is found to be sufficiently accurate for Cu and Ag while it fails for Au. The spin‐averaged Douglas‐Kroll no‐pair method gives excellent results for the studied atomic properties. The ionization potentials obtained within this method and the coupled cluster scheme for the electron correlation effects are 7.733(7.735) eV for Cu, 7.461(7.575) eV for Ag, and 9.123(9.225) eV for Au (experimental values given in parentheses). The calculated (experimental) electron affinity results for Cu, Ag, and Au are 1.236(1.226), 1.254(1.303), and 2.229(2.309) eV, respectively. There is a marked relativistic effect on both the ionization potential and electron affinity of Ag which sharply increases for Au while Cu exhibits only a little relativistic character. A similar pattern of relativistic effects is also observed for electric dipole polarizabilities of the coinage metal atoms and their ions. The coupled cluster dipole polarizabilities of the coinage metal atoms calculated in this article in the Douglas‐Kroll no‐pair formalism (Cu: 46.50 au; Ag: 52.46 au; Au: 36.06 au) are compared with our earlier data for their singly positive and singly negative ions. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 557–565, 1997