CONTRIBUTION TO THE ELECTRON-DISTRIBUTION ANALYSIS .1. SHELL STRUCTURE OF ATOMS

被引:106
作者
KOHOUT, M
SAVIN, A
PREUSS, H
机构
[1] Institut für Theoretische Chemie, Universität Stuttgart, 7000 Stuttgart 80
关键词
D O I
10.1063/1.460989
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Relativistic spherically averaged numerical all-electron densities rho were computed for the atoms Be-Ba, B-Tl, C-Pb, Cu-Au, and Zn-Hg. The Laplacian of these densities is not able to resolve the valence shell from the inner shells in case of heavy atoms, starting with the fourth row. The distribution of the local kinetic energy E(kin) shows a valence maximum even for these heavy atoms, unfortunately, in a region of negative kinetic energy; i.e., nonclassically allowed. The quantity - \NABLA-rho\/rho-was also investigated. For all computed atoms, the - \NABLA-rho\/rho diagrams are capable of describing the complete shell structure. - \NABLA-rho\/rho is sensitive to basis set quality: poor Gaussian basis sets exhibit spurious oscillations and a premature onset of the linear decay. For the atoms B-Tl, Ba, Au, Hg, and Pb, nonrelativistic numerical calculations were performed to examine the effect of the relativity on the aforementioned quantities. Tests with pseudopotential densities reveal that for pseudopotential calculations, it is advisable to use at least two outermost shells in order to reproduce the all-electron values of NABLA-2-rho, E(kin), and - \NABLA-rho\/rho in the valence region.
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页码:1928 / 1942
页数:15
相关论文
共 31 条
[1]   THE CHARACTERIZATION OF ATOMIC INTERACTIONS [J].
BADER, RFW ;
ESSEN, H .
JOURNAL OF CHEMICAL PHYSICS, 1984, 80 (05) :1943-1960
[2]   BONDED AND NONBONDED CHARGE CONCENTRATIONS AND THEIR RELATION TO MOLECULAR-GEOMETRY AND REACTIVITY [J].
BADER, RFW ;
MACDOUGALL, PJ ;
LAU, CDH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (06) :1594-1605
[3]   RADIAL DENSITY-FUNCTION AND EXPECTATION VALUES FOR IONS [J].
BOYD, RJ .
CANADIAN JOURNAL OF PHYSICS, 1978, 56 (06) :780-780
[4]   RELATIVISTIC EFFECTS IN CHEMICAL-SYSTEMS [J].
CHRISTIANSEN, PA ;
ERMLER, WC ;
PITZER, KS .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1985, 36 :407-432
[5]   ATOMIC SCREENING CONSTANTS FROM SCF FUNCTIONS [J].
CLEMENTI, E ;
RAIMONDI, DL .
JOURNAL OF CHEMICAL PHYSICS, 1963, 38 (11) :2686-&
[6]  
Clementi E., 1974, Atomic Data and Nuclear Data Tables, V14, P177, DOI 10.1016/S0092-640X(74)80016-1
[7]   A PROPER ACCOUNT OF CORE-POLARIZATION WITH PSEUDOPOTENTIALS - SINGLE VALENCE-ELECTRON ALKALI COMPOUNDS [J].
FUENTEALBA, P ;
PREUSS, H ;
STOLL, H ;
VONSZENTPALY, L .
CHEMICAL PHYSICS LETTERS, 1982, 89 (05) :418-422
[8]   PSEUDOPOTENTIAL CALCULATIONS FOR ALKALINE-EARTH ATOMS [J].
FUENTEALBA, P ;
VONSZENTPALY, L ;
PREUSS, H ;
STOLL, H .
JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 1985, 18 (07) :1287-1296
[9]   AN ATOMIC MULTICONFIGURATIONAL DIRAC-FOCK PACKAGE [J].
GRANT, IP ;
MCKENZIE, BJ ;
NORRINGTON, PH ;
MAYERS, DF ;
PYPER, NC .
COMPUTER PHYSICS COMMUNICATIONS, 1980, 21 (02) :207-231
[10]   SELF-CONSISTENT MOLECULAR-ORBITAL METHODS .I. USE OF GAUSSIAN EXPANSIONS OF SLATER-TYPE ATOMIC ORBITALS [J].
HEHRE, WJ ;
STEWART, RF ;
POPLE, JA .
JOURNAL OF CHEMICAL PHYSICS, 1969, 51 (06) :2657-+