Enthalpy difference between conformations of normal alkanes: Intramolecular basis set superposition error (BSSE) in the case of n-butane and n-hexane
Enthalpy difference between conformations of normal alkanes: Intramolecular basis set superposition error (BSSE) in the case of n-butane and n-hexane
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DOI：
10.1063/1.2997349
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发表时间：
2008-10-28
影响因子：
4.4
通讯作者：
Balabin, Roman M.
中科院分区：
文献类型：
--
作者：
Balabin, Roman M.
本文讨论了高质量从头计算正构烷烃构象平衡的一个额外误差源——分子内基集叠加误差（BSSE）。以正丁烷（正丁烷）和正己烷（正己烷）为代表。采用流行的电子相关方法计算了正丁烷的反式和间扭式构象（以及正己烷的反-反-反式构象和间扭-间扭式构象）的单点能差和BSSE值：二阶Moller-Plesset (MP2)，四阶Moller-Plesset (MP4)，以及具有非迭代三重激发的单取代和双取代的耦合簇[CCSD(T)]理论水平。外推到完整的基集被应用。bse校正和未校正的相对能量值之间的差异范围从类似于100 cal/mol（在正丁烷的情况下）到超过1000 cal/mol（在正己烷的情况下）。讨论了基集类型（people或Dunning）和尺寸[最大6-311G（3df, 3pd）和aug-cc-pVQZ]的影响。(C) 2008年美国物理研究所。(DOI: 10.1063/1.2997349)
In this paper, an extra error source for high-quality ab initio calculation of conformation equilibrium in normal alkanes-intramolecular basis set superposition error (BSSE) - is discussed. Normal butane (n-butane) and normal hexane (n-hexane) are used as representative examples. Single-point energy difference and BSSE values of trans and gauche conformations for n-butane (and trans-trans-trans and gauche-gauche-gauche conformations for n-hexane) were calculated using popular electron correlation methods: The second-order Moller-Plesset (MP2), the fourth-order Moller-Plesset (MP4), and coupled cluster with single and double substitutions with noniterative triple excitation [CCSD(T)] levels of theory. Extrapolation to the complete basis set is applied. The difference between BSSE-corrected and uncorrected relative energy values ranges from similar to 100 cal/mol (in case of n-butane) to more than 1000 cal/mol (in case of n-hexane). The influence of basis set type (Pople or Dunning) and size [up to 6-311G(3df, 3pd) and aug-cc-pVQZ] is discussed. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2997349]