Assessing the performance of ab initio classical valence bond methods for hydrogen transfer reactions

Karach, Itay; Botvinik, Alina; Truhlar, Donald G.; Wu, Wei; Shurki, Avital

doi:10.1016/j.comptc.2017.05.031

Cited by 6 publications

(4 citation statements)

References 67 publications

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“…Quantitatively, VBT is improving very fast and is starting to inspire other methods. Thus, a recent benchmark of modern VB methods by Shurki et al [ 174 ] showed that methods like VBCI, BOVB, and VBPT2 exhibit mean unsigned errors as low as 4.5–1.3 kcal/mol, very close to high-level MO-based treatments.…”

Section: Modern Conceptual Approaches In Vbtmentioning

confidence: 99%

Valence Bond Theory—Its Birth, Struggles with Molecular Orbital Theory, Its Present State and Future Prospects

2021

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This essay describes the successive births of valence bond (VB) theory during 1916–1931. The alternative molecular orbital (MO) theory was born in the late 1920s. The presence of two seemingly different descriptions of molecules by the two theories led to struggles between the main proponents, Linus Pauling and Robert Mulliken, and their supporters. Until the 1950s, VB theory was dominant, and then it was eclipsed by MO theory. The struggles will be discussed, as well as the new dawn of VB theory, and its future.

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Section: Modern Conceptual Approaches In Vbtmentioning

confidence: 99%

Valence Bond Theory—Its Birth, Struggles with Molecular Orbital Theory, Its Present State and Future Prospects

2021

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“…Instead of involving all the CSFs in the active space, the VBSCF wave function is compact and can serve as a good reference for adding dynamic correlation. The VB methods involving dynamic correlation include valence bond perturbation theory (VBPT2) − and valence bond configuration interaction (VBCI) , methods, with the VBSCF wave function as a reference.…”

Section: Introductionmentioning

confidence: 99%

Hybrid Density Functional Valence Bond Method with Multistate Treatment

Wu,

Cao,

Zhou

et al. 2024

J. Chem. Theory Comput.

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Recently, a hybrid density functional valence bond (VB) method, λ-DFVB(U), has been proposed and shown to give accuracy that is comparable to that of CASPT2 in calculations of atomization energies, atomic excitation energies, and reaction barriers, while its computational cost is approximately the same as the valence bond self-consistent-field (VBSCF) method. However, the interaction between electronic states is not included in λ-DFVB(U) since the last step of λ-DFVB(U) is not a diagonalization of the Hamiltonian matrix on the electronic state basis. Therefore, λ-DFVB(U) gives the wrong topology of the potential energy surfaces (PESs) near the conical intersection region. In the present paper, we propose a novel hybrid density functional VB method with multistate treatment, named λ-DFVB(MS), in which an effective Hamiltonian matrix is constructed on the basis of the diabatic states obtained by the valence-bond-based compression approach for the diabatization scheme, and the interaction between electronic states can be included through the diagonalization of the effective Hamiltonian matrix. Test calculations show that λ-DFVB(MS) gives the correct topology of the PESs near the conical intersection region. We also show that the VBSCF wave function with selected VB structures can be applied as a reference in λ-DFVB(MS).

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“…The second category focuses on the spin coupling patterns in VB structures and uses delocalized AOs to pursue the compactness of wave functions. Spin‐couple valence bond and generalized valence bond methods are two outstanding examples in this category, where the former uses nonorthogonal overlap‐enhanced AOs while the latter imposes strong orthogonality condition on delocalized orbitals. The third category is based on MOs and retraces VB concepts quantitatively by imposing the localization on MOs (thus orbitals are essentially semi‐delocalized).…”

Section: Introductionmentioning

confidence: 99%

“…Thus, it becomes necessary and timely to assess the performance of VB methods by using some well‐defined standard sets. Recently, Shurki and coworkers assessed the performance of ab initio classical VB methods for hydrogen transfer reactions, in which various VB methods, including valence bond self‐consistent field (VBSCF), breathing orbitals valence bond, valence bond configuration interaction (VBCI), and valence bond second‐order perturbation theory (VBPT2), were applied to three hydrogen transfer reactions taken from the HTBH6 data set of Truhlar and coworkers with reaction barrier heights derived and compared.…”

Section: Introductionmentioning

confidence: 99%

Performance of the VBSCF method for pericyclic and π bond shift reactions

Zhang

Zhou

et al. 2018

J Comput Chem

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The performance of the valence bond self-consistent field (VBSCF) method was investigated in this paper by predicting the activation barriers and reaction energies in pericyclic and π bond shift reactions for hydrocarbons. The benchmarking set includes 3 electrocyclic reactions, 3 sigmatropic shifts, 3 cycloadditions, 2 cycloreversions, and 7 π bond shift reactions, where the first 11 reactions are taken from Houk's standard set (J. Phys. Chem. A 2003, 107, 11445). Computational results reveal that the VB(CI) method, which performs VBSCF calculations first with full covalent structures and then includes all mono-and di-ionic structures to compute the total energy without further orbital optimization, matches the accuracy of the complete active space SCF (CASSCF) method very well. The mean absolute error values (the deviations from the CASSCF data) are 0.01 kcal/mol for the reaction energy, and 0.26 and 0.32 kcal/ mol for the activation energy with the 6-31G and 6-31G(d) basis sets, respectively.

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Assessing the performance of ab initio classical valence bond methods for hydrogen transfer reactions

Cited by 6 publications

References 67 publications

Valence Bond Theory—Its Birth, Struggles with Molecular Orbital Theory, Its Present State and Future Prospects

Valence Bond Theory—Its Birth, Struggles with Molecular Orbital Theory, Its Present State and Future Prospects

Hybrid Density Functional Valence Bond Method with Multistate Treatment

Performance of the VBSCF method for pericyclic and π bond shift reactions

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