Combined quantum mechanical and Molecular mechanics studies of the electron-transfer reactions involving carbon tetrachloride in solution

Marat Valiev, Eric J. Bylaska, Michel Dupuis, Paul Tratnyek

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The reductive dechlorination of carbon tetrachloride, CCl4, by a concerted electron transfer-bond breaking mechanism was studied using combined high level quantum mechanical and molecular mechanics (QM/ MM) approach. The free energy activation barriers for the first electron-transfer step were determined from the dissociation profiles of CCl4 and CCl 4 - complexes in aqueous phase using hybrid-free energy QM/MM methodologies. Both density functional and coupled cluster perturbative triples (CCSD(T)) versions of QM/ MM methods were investigated. The impact of the implicit solvent description based on continuum (COSMO) solvent models was also analyzed. QM/MM calculations at the CCSD(T)/aug-cc-pVDZ/SPCE level of theory predict that the activation barriers vary from 0.7 to 35.2 kcal/mol for -2.32 and 0.93 V reduction potentials respectively. Good agreement with experimental data for oxide-free iron electrodes (-0.6 to -1.2 V reduction potentials) is observed indicating that the measured activation barriers are consistent with the concerted electron transfer-bond-breaking mechanism.

Original languageEnglish (US)
Pages (from-to)2713-2720
Number of pages8
JournalJournal of Physical Chemistry A
Volume112
Issue number12
DOIs
StatePublished - Mar 27 2008

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Molecular mechanics
Carbon Tetrachloride
carbon tetrachloride
electron transfer
Chemical activation
activation
Free energy
Electrons
free energy
Dechlorination
Oxides
Iron
dissociation
methodology
continuums
iron
Electrodes
electrodes
oxides
profiles

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Combined quantum mechanical and Molecular mechanics studies of the electron-transfer reactions involving carbon tetrachloride in solution. / Valiev, Marat; Bylaska, Eric J.; Dupuis, Michel; Tratnyek, Paul.

In: Journal of Physical Chemistry A, Vol. 112, No. 12, 27.03.2008, p. 2713-2720.

Research output: Contribution to journalArticle

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