Ab initio QM/MM simulations with a molecular orbital‐valence bond (MOVB) method: application to an SN2 reaction in water

Mo, Yirong; Gao, Jiali

doi:10.1002/1096-987x(200012)21:16<1458::aid-jcc4>3.3.co;2-u

Cited by 92 publications

(264 citation statements)

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“…[18][19][20][21][22] Having been so extensively studied, by both experimental [23][24][25][26][27] and computational [28][29][30][31][32][33][34][35][36] means, lends this class of reactions to be an outstanding starting position for benchmarking and refining new computational methods and techniques. In particular, the chloride/methyl chloride reaction is a strong candidate as a prototype reaction as it has been quite extensively studied in order to understand the exact nature of the transition state in the gas and condensed phases.…”

Section: Introductionmentioning

confidence: 99%

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

Kuechler

York

2014

The Journal of Chemical Physics

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The nucleophilic attack of a chloride ion on methyl chloride is an important prototype S N 2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models. © 2014 AIP Publishing LLC. [http://dx

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Section: Introductionmentioning

confidence: 99%

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

Kuechler

York

2014

The Journal of Chemical Physics

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“…103,104 Importantly, solvent effects can be incorporated in the MOVB method. Thus, the MOVB method has been used to model the proton transfer between ammonium ion and ammonia in water, 102 as well as a solvated S N 2 reaction, 105 using Monte Carlo simulations.…”

Section: The Block-localized Wavefunction Methodsmentioning

confidence: 99%

A survey of recent developments in ab initio valence bond theory

Hiberty

Shaik

2006

J Comput Chem

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Starting from the 1980s and onwards, Valence Bond theory has been enjoying renaissance that is characterized by the development of a growing number of ab initio methods, and by many applications to chemical reactivity and to the central paradigms of chemistry. Owing the increase of computational power of modern computers and to significant advances in the methodology, valence bond theory begins to offer a sound and attractive alternative to Molecular Orbital theory. This review aims at summarizing the most important developments of ab initio valence bond methods during the last two or three decades, and is primarily devoted to a description of what the various methods can actually achieve within their specific scopes and limitations. Key available softwares are surveyed.

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“…Instead of "donor" and "acceptor" electronic states, one posits "product" and "reactant" diabats that exist at all points along the reaction coordinate. This diabatic framework is the basis of empirical VB theory [16,17] and has been used to analyze S N 1 [47] and S N 2 [112] reactions, as well as proton transfer [21]. Once the diabatic states are defined, one is typically interested in computing the corresponding adiabatic energies by solving the generalized eigenvalue problem in Eq.…”

Section: Explicit Solventmentioning

confidence: 99%

The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics

Voorhis

Kowalczyk

Kaduk

et al. 2010

Annu. Rev. Phys. Chem.

296

366

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Diabatic states have a long history in chemistry, beginning with early valence bond pictures of molecular bonding and stretching through the construction of model potential energy surfaces to the modern proliferation of methods for computing these elusive states. In this review we summarize the basic principles that define the diabatic basis and demonstrate how they can be applied in the specific context of constrained density functional theory. Using illustrative examples from electron transfer and chemical reactions, we show how the diabatic picture can be used to extract qualitative insight and quantitative predictions about energy landscapes. The review closes with a brief resumé of the challenges and prospects for the further application of diabatic states in chemistry.

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Ab initio QM/MM simulations with a molecular orbital‐valence bond (MOVB) method: application to an SN2 reaction in water

Cited by 92 publications

References 0 publications

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

A survey of recent developments in ab initio valence bond theory

The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics

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