ISSN:
1432-2234
Schlagwort(e):
Copper
;
Excited electronic states
;
Relativistic wavefunctions
Quelle:
Springer Online Journal Archives 1860-2000
Thema:
Chemie und Pharmazie
Notizen:
Summary The2 S g (d 10 s 1),2 D g (d 9 s 2),2 P u (d 10 p 1),2,4{F,P} u (d 9 s 1 p 1) states of copper as well as the1 S g (d 10) state of the positive copper ion are studied byab initio methods. Relativistic wavefunctions are determined variationally solving a one-component no-pair equation. This approximation makes it possible to treat all the states in a common set of orbitals. It is found that differential relativistic effects for the excitation energies are independent of the one-particle basis employed. The first-order perturbation estimate using the mass-velocity and Darwin operators depends critically on the description of the 3s and 3p core electrons. Among the various one-particle sets tested,2 D g orbitals, with the (4s, 4p) near-degeneracy effects included in the orbital optimization step, are most appropriate for the correlation treatment. They give an error of 0.3 eV for the2 S g –2 D g separation only slightly inferior to our best result employing parent orbitals for both states. All other states agree with experiment to within 0.2 eV. The first-order spin-orbit splitting of the2 D g state (−2006 cm−1) is in excellent agreement with the experimental value.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1007/BF01134862
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