Density functional calculations of electronic g-tensors using spin-orbit pseudopotentials and mean-field all-electron spin-orbit operators

被引:194
作者
Malkina, OL
Vaara, J
Schimmelpfennig, B
Munzarová, M
Malkin, VG
Kaupp, M
机构
[1] Slovak Acad Sci, Inst Inorgan Chem, SK-84236 Bratislava, Slovakia
[2] Slovak Acad Sci, Ctr Comp, SK-84236 Bratislava, Slovakia
[3] Max Planck Inst Festkorperforsch, D-70569 Stuttgart, Germany
[4] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany
关键词
D O I
10.1021/ja000984s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Modern density-functional methods for the calculation of electronic g-tensors have been implemented within the framework of the deMon code. All relevant perturbation operators are included. Particular emphasis has been placed on accurate yet efficient treatment of the two-electron spin-orbit terms. At an all-electron level, the computationally inexpensive atomic mean-field approximation is shown to provide spin-orbit contributions in excellent agreement with the results obtained using explicit one- and two-electron spin-orbit integrals. Spin-other-orbit contributions account for up to 25-30% of the two-electron terms and may thus be non-negligible. For systems containing heavy atoms we use a pseudopotential treatment, where quasirelativistic pseudopotentials are included in the Kohn-Sham calculation whereas appropriate spin-orbit pseudopotentials are used in the perturbational treatment of the g-tensors. This approach is shown to provide results in good agreement with the all-electron treatment, at moderate computational cost. Due to the atomic nature of both mean-field all-electron and pseudopotential spin-orbit operators used, the two approaches may even be combined in one calculation. The atomic character of the spin-orbit operators may also be used to analyze the contributions of certain atoms to the paramagnetic terms of the g-tensors. The new methods have been applied to a wide variety of species, including small main group systems, aromatic radicals, as well as transition metal complexes.
引用
收藏
页码:9206 / 9218
页数:13
相关论文
共 75 条
[1]   Characterization of a new tyrosyl free radical in Salmonella typhimurium ribonucleotide reductase with EPR at 9.45 and 245 GHz [J].
Allard, P ;
Barra, AL ;
Andersson, KK ;
Schmidt, PP ;
Atta, M ;
Graslund, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (04) :895-896
[2]   ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 2ND AND 3RD ROW TRANSITION-ELEMENTS [J].
ANDRAE, D ;
HAUSSERMANN, U ;
DOLG, M ;
STOLL, H ;
PREUSS, H .
THEORETICA CHIMICA ACTA, 1990, 77 (02) :123-141
[3]   CONTRIBUTION OF THE RELATIVISTIC MASS CORRECTION TO THE G TENSOR OF MOLECULES [J].
ANGSTL, R .
CHEMICAL PHYSICS, 1989, 132 (03) :435-442
[4]  
[Anonymous], 1971, APPROXIMATE ATOMIC F
[5]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[6]   Simulation of delocalized exchange by local density functionals [J].
Becke, AD .
JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (09) :4020-4026
[7]   DENSITY-FUNCTIONAL STUDY OF MAGNETIC COUPLING PARAMETERS - RECONCILING THEORY AND EXPERIMENT FOR THE TIF3 COMPLEX [J].
BELANZONI, P ;
BAERENDS, EJ ;
VANASSELT, S ;
LANGEWEN, PB .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (35) :13094-13102
[8]   AB-INITIO ENERGY-ADJUSTED PSEUDOPOTENTIALS FOR ELEMENTS OF GROUPS 13-17 [J].
BERGNER, A ;
DOLG, M ;
KUCHLE, W ;
STOLL, H ;
PREUSS, H .
MOLECULAR PHYSICS, 1993, 80 (06) :1431-1441
[9]  
Boys S. F., 1966, Quantum theory of atoms, molecules, and the solid state, P253
[10]   Density functional computations of transition metal NMR chemical shifts: Dramatic effects of Hartree-Fock exchange [J].
Buhl, M .
CHEMICAL PHYSICS LETTERS, 1997, 267 (3-4) :251-257