Atomic reference energies for density functional calculations

被引:165
作者
Baerends, EJ [1 ]
Branchadell, V [1 ]
Sodupe, M [1 ]
机构
[1] UNIV AUTONOMA BARCELONA,DEPT QUIM,BELLATERRA 08193,SPAIN
关键词
D O I
10.1016/S0009-2614(96)01449-2
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
Atomic ground states are usually degenerate. It is demonstrated that the density functionals for the exchange-correlation energy that are commonly used are not invariant over the set of ground state densities. This leads to uncertainties of the order of 3 to 5 kcal/mol in the atomic ground state energy of second and third period main group elements and the first transition series. A much larger spread in energies is obtained for transition elements if symmetry and equivalence restrictions for the Kohn-Sham orbitals are abandoned. It is recommended that atomic ground states that are actually used to calculate heats of atomization are made explicit, and tables with one choice of atomic ground state energies for the first rows of the periodic system are provided for the local density approximation and for a few generalized gradient approximations.
引用
收藏
页码:481 / 489
页数:9
相关论文
共 34 条
[1]  
[Anonymous], [No title captured], DOI DOI 10.1016/0021-9991(92)90277-6
[2]   STEEPEST-DESCENT DETERMINATION OF OCCUPATION NUMBERS AND ENERGY MINIMIZATION IN THE LOCAL-DENSITY APPROXIMATION [J].
AVERILL, FW ;
PAINTER, GS .
PHYSICAL REVIEW B, 1992, 46 (04) :2498-2502
[3]   Self-consistent molecular Hartree-Fock-Slater calculations - I. The computational procedure [J].
Baerends, E. J. ;
Ellis, D. E. ;
Ros, P. .
CHEMICAL PHYSICS, 1973, 2 (01) :41-51
[4]  
BAERENDS EJ, 1978, INT J QUANTUM CHEM, V12, P169
[5]   DENSITY FUNCTIONAL CALCULATIONS OF MOLECULAR-BOND ENERGIES [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1986, 84 (08) :4524-4529
[6]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[7]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[8]   LOCAL EXCHANGE-CORRELATION APPROXIMATIONS AND 1ST-ROW MOLECULAR DISSOCIATION-ENERGIES [J].
BECKE, AD .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1985, 27 (05) :585-594
[9]   3-DIMENSIONAL NUMERICAL-INTEGRATION FOR ELECTRONIC-STRUCTURE CALCULATIONS [J].
BOERRIGTER, PM ;
VELDE, GT ;
BAERENDS, EJ .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1988, 33 (02) :87-113
[10]   DENSITY-FUNCTIONAL THEORY APPLIED TO THE EXCITED-STATES OF COORDINATION-COMPOUNDS [J].
DAUL, C .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1994, 52 (04) :867-877