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Ionization potentials and electron affinities of Cu, Ag, and Au: Electron correlation and relativistic effects

1997; Wiley; Volume: 63; Issue: 2 Linguagem: Inglês

10.1002/(sici)1097-461x(1997)63

1097-461X

Pavel Neogr�dy, Vladimir Kell�, Miroslav Urban, Andrzej J. Sadlej,

Atomic and Molecular Physics

International Journal of Quantum ChemistryVolume 63, Issue 2 p. 557-565 Properties, Dynamics, and Electronic Structure of Atoms and Molecules Ionization potentials and electron affinities of Cu, Ag, and Au: Electron correlation and relativistic effects Pavel Neogrády, Pavel Neogrády Department of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaSearch for more papers by this authorVladimir Kellö, Vladimir Kellö Department of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaSearch for more papers by this authorMiroslav Urban, Corresponding Author Miroslav Urban Department of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaDepartment of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaSearch for more papers by this authorAndrzej J. Sadlej, Andrzej J. Sadlej Department of Theoretical Chemistry, Chemical Centre, University of Lund, P.O.B. 124, S-221 00 Lund, SwedenSearch for more papers by this author Pavel Neogrády, Pavel Neogrády Department of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaSearch for more papers by this authorVladimir Kellö, Vladimir Kellö Department of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaSearch for more papers by this authorMiroslav Urban, Corresponding Author Miroslav Urban Department of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaDepartment of Physical Chemistry, Faculty of Sciences, Comenius University, Mlynska dolina, SK-842 15 Bratislava, SlovakiaSearch for more papers by this authorAndrzej J. Sadlej, Andrzej J. Sadlej Department of Theoretical Chemistry, Chemical Centre, University of Lund, P.O.B. 124, S-221 00 Lund, SwedenSearch for more papers by this author First published: 06 December 1998 https://doi.org/10.1002/(SICI)1097-461X(1997)63:2 3.0.CO;2-3Citations: 88AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract 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 Citing Literature Volume63, Issue21997Pages 557-565 RelatedInformation