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辅助密度泛函理论杂化计算对周环反应活化能和反应焓的准确性。

Accuracy of auxiliary density functional theory hybrid calculations for activation and reaction enthalpies of pericyclic reactions.

作者信息

Gómez-Pérez José R, Delesma Francisco A, Calaminici Patrizia, Köster Andreas M

机构信息

Departamento de Química, CINVESTAV, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, A.P. 14-740, 07000, México D.F, Mexico.

Programa de Doctorado en Nanociencias y Nanotecnología, CINVESTAV, Instituto Politécnico Nacional 2508, A.P. 14-740, 07000, Ciudad de México, Mexico.

出版信息

J Mol Model. 2018 Aug 4;24(9):223. doi: 10.1007/s00894-018-3759-8.

DOI:10.1007/s00894-018-3759-8
PMID:30078124
Abstract

Auxiliary density functional theory (ADFT) hybrid calculations are based on the variational fitting of the Coulomb and Fock potential and, therefore, are free of four-center electron repulsion integrals. So far, ADFT hybrid calculations have been validated successfully for standard enthalpies of formation. In this work the accuracy of ADFT hybrid calculations for the description of pericyclic reactions was quantitatively validated at the B3LYP/6-31G*/GEN-A2* level of theory. Our comparison with conventional Kohn-Sham density functional theory (DFT) results shows that the DFT and ADFT activation and reaction enthalpies are practically indistinguishable. A systematic study of various functionals (PBE, B3LYP, PBE0, CAMB3LYP, CAMPBE0 and HSE06) and basis sets (6-31G*, DZVP-GGA and aug-cc-pVXZ; X = D, T and Q) revealed that the ADFT HSE06/aug-cc-pVTZ/GEN-A2* level of theory yields best balanced accuracy for the activation and reaction enthalpies of the studied pericyclic reactions. With the successfully validate ADFT composite approach consisting of PBE/DZVP-GGA/GEN-A2* structure and transition state optimizations and single-point HSE06/aug-cc-pVTZ/GEN-A2* energy calculations, an accurate, reliable and efficient computational approach for the study of pericyclic reactions in systems at the nanometer scale is proposed.

摘要

辅助密度泛函理论（ADFT）杂化计算基于库仑势和福克势的变分拟合，因此不存在四中心电子排斥积分。到目前为止，ADFT杂化计算已成功验证了标准生成焓。在这项工作中，在B3LYP/6 - 31G*/GEN - A2理论水平下对ADFT杂化计算描述周环反应的准确性进行了定量验证。我们与传统的科恩 - 沈密度泛函理论（DFT）结果的比较表明，DFT和ADFT的活化能和反应焓实际上难以区分。对各种泛函（PBE、B3LYP、PBE0、CAMB3LYP、CAMPBE0和HSE06）和基组（6 - 31G、DZVP - GGA和aug - cc - pVXZ；X = D、T和Q）的系统研究表明，ADFT的HSE06/aug - cc - pVTZ/GEN - A2理论水平对于所研究周环反应的活化能和反应焓产生了最佳平衡的准确性。通过成功验证由PBE/DZVP - GGA/GEN - A2结构和过渡态优化以及单点HSE06/aug - cc - pVTZ/GEN - A2*能量计算组成的ADFT复合方法，提出了一种用于研究纳米尺度系统中周环反应的准确、可靠且高效的计算方法。

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