Partial Hessian vibrational analysis: the localization of the molecular vibrational energy and entropy |
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Authors: | Hui Li Jan H Jensen |
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Institution: | (1) Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA, US |
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Abstract: | 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.
Received: 21 September 2001 / Accepted: 30 October 2001 / Published online: 22 March 2002 |
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Keywords: | : Ab initio – Hessians – Vibrational analysis – Constrained optimizations – Quantum mechanics/ molecular mechanics |
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