Modified local exchange and kinetic energy functionals for atomic systems

被引:4
作者
Fuentealba, P [1 ]
机构
[1] UNIV CHILE, FAC CIENCIAS, CTR MECAN CUANT APLICADA, SANTIAGO, CHILE
来源
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 1997年 / 390卷
关键词
density functional theory; exchange energy functional; kinetic energy functional;
D O I
10.1016/S0166-1280(96)04753-7
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
New local functionals for the kinetic and Hartree-Fock exchange energy of atoms are proposed. They are of the following general form: T[p] = 2(2/3)C(F) integral Sigma(sigma)rho(sigma)(5/3)f(r(pi)o(sigma))dr, and E(x)[p] = -2(1/3)C(x) integral Sigma(Sigma)rho(sigma)(4/3)(r,rho(sigma))dr. The function f(r, p,), except for two adjustable parameters, is the same for both functionals. They are constructed to distinguish between non-uniform scaling along different coordinates. The functionals are tested and compared with other commonly used functionals for neutral atoms He to Ar. The exchange energy functional is also tested through Kohn-Sham self-consistent calculations for atoms and ions. Total and exchange energies for hydrogen to argon atoms and for the helium and beryllium isoelectronic series are presented and compared with local density approximation (LDA) and Hartree-Fock (HF) results. The first ionization potential of the atoms of the second row of the periodic table are also calculated. In addition, for the atoms Cr, Mn and As the eigenvalues of the highest occupied orbital are also calculated and compared with other results. It is shown that the new proposed functionals present in all cases a clearly improvement over the LDA approximation and they are comparable in accuracy with the generalized gradient corrected functionals.
引用
收藏
页码:1 / 9
页数:9
相关论文
共 34 条
[1]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[2]   EXPONENTIAL APPROXIMATION FOR THE DENSITY-MATRIX AND THE WIGNER DISTRIBUTION [J].
BERKOWITZ, M .
CHEMICAL PHYSICS LETTERS, 1986, 129 (05) :486-488
[3]   ROOTHAAN-HARTREE-FOCK GROUND-STATE ATOMIC WAVE-FUNCTIONS - SLATER-TYPE ORBITAL EXPANSIONS AND EXPECTATION VALUES FOR Z=2-54 [J].
BUNGE, CF ;
BARRIENTOS, JA ;
BUNGE, AV .
ATOMIC DATA AND NUCLEAR DATA TABLES, 1993, 53 (01) :113-162
[4]  
Clementi E., 1974, Atomic Data and Nuclear Data Tables, V14, P177, DOI 10.1016/S0092-640X(74)80016-1
[5]   KINETIC-ENERGY FUNCTIONALS VIA PADE APPROXIMATIONS [J].
DEPRISTO, AE ;
KRESS, JD .
PHYSICAL REVIEW A, 1987, 35 (01) :438-441
[6]   RATIONAL-FUNCTION REPRESENTATION FOR ACCURATE EXCHANGE ENERGY FUNCTIONALS [J].
DEPRISTO, AE ;
KRESS, JD .
JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (03) :1425-1428
[7]  
DREIZLER RM, 1990, DENSITY FUNCTIONAL M
[8]   ACCURATE OPTIMIZED-POTENTIAL-MODEL SOLUTIONS FOR SPHERICAL SPIN-POLARIZED ATOMS - EVIDENCE FOR LIMITATIONS OF THE EXCHANGE-ONLY LOCAL SPIN-DENSITY AND GENERALIZED-GRADIENT APPROXIMATIONS [J].
ENGEL, E ;
VOSKO, SH .
PHYSICAL REVIEW A, 1993, 47 (04) :2800-2811
[9]   ASYMPTOTIC PROPERTIES OF THE EXCHANGE ENERGY DENSITY AND THE EXCHANGE POTENTIAL OF FINITE SYSTEMS - RELEVANCE FOR GENERALIZED GRADIENT APPROXIMATIONS [J].
ENGEL, E ;
CHEVARY, JA ;
MACDONALD, LD ;
VOSKO, SH .
ZEITSCHRIFT FUR PHYSIK D-ATOMS MOLECULES AND CLUSTERS, 1992, 23 (01) :7-14
[10]   FURTHER EVIDENCE OF THE CONJOINT CORRECTION TO THE LOCAL KINETIC AND EXCHANGE ENERGY DENSITY FUNCTIONALS [J].
FUENTEALBA, P ;
REYES, O .
CHEMICAL PHYSICS LETTERS, 1995, 232 (1-2) :31-34