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Extension of the "Cheap" Composite Approach to Noncovalent Interactions: The jun-ChS Scheme.
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2020-01-07 , DOI: 10.1021/acs.jctc.9b01037
Silvia Alessandrini 1, 2 , Vincenzo Barone 1 , Cristina Puzzarini 2
Affiliation  

A new variant of the so-called "cheap" composite scheme has been purposely developed for the evaluation of the interaction energy of noncovalent molecular complexes, with its various contributions being tested for a set of 15 systems using the accurate interaction energies reported as reference values in the following: [ Řezáč, J. et al. Phys. Chem. Chem. Phys. 2015 , 17 , 19268 - 19277 ]. The modified scheme, starting from the CCSD(T) method in conjunction with a triple-ζ-quality basis set augmented by diffuse functions, includes two additional terms computed at the MP2 level: (i) the extrapolation to the complete basis set (CBS) limit and (ii) the contribution of core-valence correlation effects (CV term). Various families of basis sets including diffuse functions have been tested for the CCSD(T) model as well as for the extrapolation to the CBS limit, with a mean absolute error of about 1% (below 0.2 kJ·mol-1 in absolute terms) obtained with the jun-cc-pVnZ and the jul-cc-pVnZ families. As far as the CV term is concerned, the cc-pCVTZ and cc-pwCVTZ basis sets provide comparable contributions, which are non-negligible in several cases. While the benchmark analysis has been carried out using accurate structures available in the literature, geometrical effects due to the use of reference B2PLYP(-D3BJ) geometries, optimized in conjunction with a triple-ζ-quality basis set, have been investigated, thus pointing out their suitability. Finally, the modified scheme has been applied to a number of test cases for which interaction energies were already available in the literature; among these, a number of molecular complexes bearing second-row atoms have been considered.

中文翻译:

将“便宜”的复合方法扩展到非共价相互作用:jun-ChS计划。

为了评估非共价分子复合物的相互作用能,专门开发了所谓的“便宜”复合方案的新变体,使用报告的准确相互作用能作为一组参考值,对一组15个系统的各种贡献进行了测试。在以下内容中:[Řezáč,J.等。物理 化学 化学 物理 2015,17,19268-19277]。修改后的方案从CCSD(T)方法开始,结合由扩散函数增强的三重ζ质量基础集,包括在MP2级别上计算出的两个附加项:(i)外推到完整基础集(CBS) )限制和(ii)核心价相关效应的贡献(CV术语)。对于CCSD(T)模型以及外推到CBS极限,已经测试了包括扩散函数在内的各种基础集,其平均绝对误差约为1%(绝对值低于0.2 kJ·mol-1)。是从jun-cc-pVnZ和jul-cc-pVnZ系列获得的。就CV术语而言,cc-pCVTZ和cc-pwCVTZ基集提供了可比较的贡献,在某些情况下不可忽略。虽然已使用文献中提供的精确结构进行了基准分析,但已经研究了由于使用参考B2PLYP(-D3BJ)几何结构(结合三重ζ质量基础集而进行了优化)而产生的几何效应,因此指出了排除它们的适用性。最后,修改后的方案已应用于许多测试案例,这些案例的相互作用能已经在文献中得到了证明;其中,已经考虑了许多带有第二行原子的分子配合物。
更新日期:2020-01-07
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