Classical Valence Bond Approach by Modern Methods

Wu, Wei; Su, Peifeng; Shaik, Sason; Hiberty, Philippe C.

doi:10.1021/cr100228r

Cited by 239 publications

(227 citation statements)

References 291 publications

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“…Mixing of all of the structures above (also termed diabatic states) results in adiabatic states, the lowest of which describes the reaction profile (bold curve in Fig. 1C scheme which is often used (see 11,13 and references cited therein):…”

Section: Learning Box 2 Constructing a Vb Wavefunctionmentioning

confidence: 99%

“…In this review we will focus on the original VB approach (see refs. 11 and references cited therein). Its 50 building blocks are VB structures, some of which are equivalent to the well-known Lewis structures.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, recent developments involve various ab-initio VB approaches that incorporate dynamic correlation. 11 These include for example: (1) The BOVB where the average field restriction of the VBSCF is removed and a unique set of 60 orbitals for each VB structure is allowed. 16 (2) The VBCI approach, where the configuration interaction (CI) procedure follows a VBSCF calculation, where replacing occupied VB orbitals by virtual VB orbitals that share the same locality produces excited configurations (see ref.…”

mentioning

confidence: 99%

“…16 (2) The VBCI approach, where the configuration interaction (CI) procedure follows a VBSCF calculation, where replacing occupied VB orbitals by virtual VB orbitals that share the same locality produces excited configurations (see ref. 11 and references cited 65 therein). (3) The VBPT2 approach, which incorporates perturbation theory, where the wavefunction is given as the sum of zeroth-order wavefunction obtained at the VBSCF level and the first-order wavefunction given as a linear combination of the singly and doubly excited structures (see ref.…”

mentioning

confidence: 99%

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How valence bond theory can help you understand your (bio)chemical reaction

et al. 2015

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Section: Learning Box 2 Constructing a Vb Wavefunctionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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How valence bond theory can help you understand your (bio)chemical reaction

et al. 2015

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“…This is in contrast to the quasi-complete-active-space (QCAS) method 22 that uses a similar wavefunction ansatz. Our approach is similar in spirit to Molecular Orbital Valence Bond (MOVB) 39 and constrained DFT configuration interaction (CDFT-CI) methods in that we construct adiabatic states from a set of states that have some desired local diabatic character. 14,40 An important distinction with these methods is that we explicitly construct our states to be orthogonal.…”

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confidence: 99%

Communication: Active-space decomposition for molecular dimers

Parker¹,

Seideman²,

Ratner³

et al. 2013

The Journal of Chemical Physics

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We have developed an active-space decomposition strategy for molecular dimers that allows for the efficient computation of the dimer's complete-active-space wavefunction while only constructing the monomers’ active-space wavefunctions. Dimer states are formed from linear combinations of direct products of localized orthogonal monomer states and Hamiltonian matrix elements are computed directly without explicitly constructing the product space. This decomposition is potentially exact in the limit where a full set of monomer states is included. The adiabatic states are then found by diagonalizing the dimer Hamiltonian matrix. We demonstrate the convergence of our method to a complete-active-space calculation of the full dimer with two test cases: the benzene and naphthalene dimers.

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