Relativistic four-component calculations of indirect nuclear spin-spin couplings in MH4 (M=C, Si, Ge, Sn, Pb) and Pb(CH3)3H

被引：88
作者：
Enevoldsen, T
Visscher, L
Saue, T
Jensen, HJA
Oddershede, J
机构：
[1] Univ So Denmark, Dept Chem, DK-5230 Odense M, Denmark
[2] Vrije Univ Amsterdam, Dept Chem, NL-1081 HV Amsterdam, Netherlands
来源：
JOURNAL OF CHEMICAL PHYSICS | 2000年 / 112卷 / 08期
关键词：
D O I：
10.1063/1.480504
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 four-component random phase approximation (RPA) calculations of indirect nuclear spin-spin coupling constants in MH4 (M=C, Si, Ge, Sn, Pb) and Pb(CH3)(3)H are presented. The need for tight s-functions also in relativistic four-component calculations is verified and explained, and the effect of omission of (SS-LL) and (SS-SS) two-electron integrals is investigated. Already in GeH4 we see a relativistic increase in the coupling constant by 12%, and for PbH4 the effect is a 156% increase for the one-bond coupling. Large relativistic effects are also computed for the two-bonds couplings. We find that the relativistic effects on the one-bond couplings are mainly due to scalar relativistic factors rather than spin-orbit corrections. (C) 2000 American Institute of Physics. [S0021-9606(00)30408-1].
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页码：3493 / 3498
页数：6
相关论文
共 38 条
[1]   On the origin and contribution of the diamagnetic term in four-component relativistic calculations of magnetic properties [J].
Aucar, GA ;
Saue, T ;
Visscher, L ;
Jensen, HJA .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) :6208-6218
[2]   RELATIVISTIC THEORY FOR INDIRECT NUCLEAR-SPIN SPIN COUPLINGS WITHIN THE POLARIZATION PROPAGATOR APPROACH [J].
AUCAR, GA ;
ODDERSHEDE, J .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1993, 47 (06) :425-435
[3]  
Brugel W, 1979, HDB NMR SPECTRAL PAR, V13
[4]   Z DEPENDENCE OF COUPLING CONSTANTS BETWEEN DIRECTLY BONDED NUCLEI - VALUE OF J(GE-73-C-13) [J].
DALLING, DK ;
GUTOWSKY, HS .
JOURNAL OF CHEMICAL PHYSICS, 1971, 55 (10) :4959-&
[5]  
Dunning Jr T.H, 1977, METHODS ELECT STRUCT
[6]   GAUSSIAN BASIS FUNCTIONS FOR USE IN MOLECULAR CALCULATIONS .1. CONTRACTION OF (9S5P) ATOMIC BASIS SETS FOR FIRST-ROW ATOMS [J].
DUNNING, TH .
JOURNAL OF CHEMICAL PHYSICS, 1970, 53 (07) :2823-+
[7]   GRASP - A GENERAL-PURPOSE RELATIVISTIC ATOMIC-STRUCTURE PROGRAM [J].
DYALL, KG ;
GRANT, IP ;
JOHNSON, CT ;
PARPIA, FA ;
PLUMMER, EP .
COMPUTER PHYSICS COMMUNICATIONS, 1989, 55 (03) :425-456
[8]   Optimization of Gaussian basis sets for Dirac-Hartree-Fock calculations [J].
Dyall, KG ;
Faegri, K .
THEORETICA CHIMICA ACTA, 1996, 94 (01) :39-51
[9]   PROTON RESONANCE SPECTRA OF SOME DERIVATIVES OF MONOGERMANE [J].
EBSWORTH, EA ;
FRANKISS, SG ;
ROBIETTE, AG .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1964, 12 (03) :299-&
[10]   Correlated calculations of indirect nuclear spin-spin coupling constants using second-order polarization propagator approximations: SOPPA and SOPPA(CCSD) [J].
Enevoldsen, T ;
Oddershede, J ;
Sauer, SPA .
THEORETICAL CHEMISTRY ACCOUNTS, 1998, 100 (5-6) :275-284
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