Partial Hessian vibrational analysis

The localization of the molecular vibrational energy and entropy

Hui Li, Jan H. Jensen

Research output: Contribution to journalArticle

70 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)211-219
Number of pages9
JournalTheoretical Chemistry Accounts
Volume107
Issue number4
DOIs
StatePublished - Dec 1 2002

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Chemical reactions
chemical reactions
Entropy
entropy
Deprotonation
Vibrational spectra
Free energy
Enthalpy
enthalpy
free energy
fragments
harmonics
Atoms
energy
matrices
atoms

Keywords

  • Ab initio
  • Constrained optimizations
  • Hessians
  • Quantum mechanics/molecular mechanics
  • Vibrational analysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Partial Hessian vibrational analysis : The localization of the molecular vibrational energy and entropy. / Li, Hui; Jensen, Jan H.

In: Theoretical Chemistry Accounts, Vol. 107, No. 4, 01.12.2002, p. 211-219.

Research output: Contribution to journalArticle

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