Infinite basis limits in electronic structure theory
Infinite basis limits in electronic structure theory
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DOI：
10.1063/1.479659
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发表时间：
1999-08-15
影响因子：
4.4
通讯作者：
Truhlar, DG
中科院分区：
文献类型：
--
作者：
Fast, PL;Sánchez, ML;Truhlar, DG
我们已经开发了一个包含29个分子的数据库，我们已经估计了5个电子结构理论的零原子化能的完全单电子基集极限：hartri - fock （HF）理论，Moller-Plesset二阶和四阶微扰理论，基于单激发和双激发的耦合簇理论（CCSD），以及CCSD加上三重激发的准微扰处理[CCSD(T)]，所有这些都是在一个单一的标准几何集上。收敛性检验表明，估计值在cc-pVnZ基集序列n=∞极限的零点几kcal/mol范围内。然后使用该数据获得优化的幂律指数，以便从相关一致的极化价双和三重zeta （cc-pVDZ和cc-pVTZ）基集外推到基集极限。这使得人们可以获得与极化四倍或五倍zeta （cc-pVQZ或cc-pV5Z）基集相当的热化学精度，其成本与极化三倍zeta非常相似，比极化四倍zeta便宜一个数量级，比极化五倍zeta便宜两个数量级。(C) 1999年美国物理研究所。[s0021 - 9606(99) 30829 - 1]。
We have developed a database of 29 molecules for which we have estimated the complete-one-electron-basis-set limit of the zero-point-exclusive atomization energy for five levels of electronic structure theory: Hartree-Fock (HF) theory, Moller-Plesset second- and fourth-order perturbation theory, coupled cluster theory based on single and double excitations (CCSD), and CCSD plus a quasiperturbative treatment of triple excitations [CCSD(T)], all at a single set of standard geometries. Convergence checks indicate that the estimates are within a few tenths of a kcal/mol of the n=infinity limit of the cc-pVnZ basis set sequence. This data is then used to obtain optimized power-law exponents for extrapolating to the basis-set-limit from correlation-consistent polarized valence double and triple zeta (cc-pVDZ and cc-pVTZ) basis sets. This allows one to get thermochemical accuracy comparable to polarized quadruple or quintuple zeta (cc-pVQZ or cc-pV5Z) basis sets with a cost very comparable to polarized triple zeta, which is one order of magnitude less expensive than polarized quadruple zeta and two orders of magnitude less expensive than polarized quintuple zeta. (C) 1999 American Institute of Physics. [S0021-9606(99)30829-1].