2003
DOI: 10.1002/chem.200305093
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An Accurate Barrier for the Hydrogen Exchange Reaction from Valence Bond Theory: Is this Theory Coming of Age?

Abstract: One of the landmark achievements of quantum chemistry, specifically of MO-based methods that include electron correlation, was the precise calculation of the barrier for the hydrogen-exchange reaction (B. Liu, J. Chem. Phys. 1973, 58, 1925; P. Siegbahn, B. Liu, J. Chem. Phys. 1978, 68, 2457). This paper reports an accurate calculation of this barrier by two recently developed VB methods that use only the eight classical VB structures. To our knowledge, the present work is the first accurate ab initio VB barrie… Show more

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Cited by 34 publications
(33 citation statements)
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“…The breathing-orbital valence (BOVB) method [115][116][117][118][119] was devised with the aim of computing diabatic or adiabatic states with wave functions that combine the properties of compactness, unambiguous interpretability in terms of structural formulas and accuracy of the calculated energies. The following features have to be fulfilled to retain interpretability and achieve reasonably good accuracy for the BOVB method: (i) the VB structures have to be constructed with HAOs, which means that covalent and ionic forms are explicitly considered; (ii) all the VB structures that are relevant to the electronic system being computed are generated; (iii) the coefficients and orbitals of the VB structures are optimized simultaneously.…”
Section: The Breathing-orbital Valence Methodsmentioning
confidence: 99%
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“…The breathing-orbital valence (BOVB) method [115][116][117][118][119] was devised with the aim of computing diabatic or adiabatic states with wave functions that combine the properties of compactness, unambiguous interpretability in terms of structural formulas and accuracy of the calculated energies. The following features have to be fulfilled to retain interpretability and achieve reasonably good accuracy for the BOVB method: (i) the VB structures have to be constructed with HAOs, which means that covalent and ionic forms are explicitly considered; (ii) all the VB structures that are relevant to the electronic system being computed are generated; (iii) the coefficients and orbitals of the VB structures are optimized simultaneously.…”
Section: The Breathing-orbital Valence Methodsmentioning
confidence: 99%
“…This instantaneous adaptation brings some dynamic correlation that is missing at the VBSCF, GVB, SC and CASSCF levels, and results in better accuracy, as shown in benchmark calculation of bond dissociation energies and reaction barriers. 117,118 The relationship between the effect of breathing orbitals and dynamic correlation is particularly well illustrated in three-electron bonds, where all the electronic correlation is of dynamic nature. 119 The BOVB method has several levels of accuracy.…”
Section: The Breathing-orbital Valence Methodsmentioning
confidence: 99%
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