Partial Hessian vibrational analysis: the localization of the molecular vibrational energy and entropy

被引：108

作者：

Li, H ^{[1
]}

Jensen, JH ^{[1
]}

机构：

[1] Univ Iowa, Dept Chem, Iowa City, IA 52242 USA

来源：

THEORETICAL CHEMISTRY ACCOUNTS | 2002年 / 107卷 / 04期

关键词：

ab initio; Hessians; vibrational analysis; constrained optimizations; quantum mechanics/molecular mechanics;

D O I：

10.1007/s00214-001-0317-7

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 partial Hessian vibrational analysis (PHVA), in which only a subblock of the Hesssian matrix is diagonalized to yield vibrational frequencies for partially optimized systems, is extended to the calculation of vibrational enthalpy and entropy changes for chemical reactions. The utility of this method is demonstrated for various deprotonation reactions by reproducing full HVA values to within 0.1-0.4 kcal/mol, depending on the number atoms included in the PHVA. When combined with the hybrid effective fragment potential method [Gordon MS, et al. (2001) J Phys Chem A 105:293-307], the PHVA method can provide (harmonic) free-energy changes for localized chemical reactions in very large systems.

引用

页码：211 / 219

页数：9

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