Sources of error in electronic structure calculations on small chemical systems

被引:191
作者
Feller, D
Peterson, KA [1 ]
Crawford, TD
机构
[1] Washington State Univ, Dept Chem, Pullman, WA 99164 USA
[2] Virginia Polytech Inst & State Univ, Dept Chem, Blacksburg, VA 24061 USA
关键词
D O I
10.1063/1.2137323
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
The sources of error in electronic structure calculations arising from the truncation of the one-particle and n-particle expansions are examined with very large correlation consistent basis sets, in some cases up through valence 10-zeta quality, and coupled cluster methods, up through connected quadruple excitations. A limited number of full configuration interaction corrections are also considered. For cases where full configuration interaction calculations were unavailable or prohibitively expensive, a continued fraction approximation was used. In addition, errors arising from core/valence and relativistic corrections are also probed for a number of small chemical systems. The accuracies of several formulas for estimating total energies and atomization energies in the complete basis set limit are compared in light of the present large basis set findings. In agreement with previous work, the CCSD(T) method is found to provide results that are closer to the CCSDTQ and full configuration-interaction results than the less approximate CCSDT method. (c) 2006 American Institute of Physics.
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页数:17
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