A multi-state empirical valence bond model for acid–base chemistry in aqueous solution

C̆uma, Martin; Schmitt, Udo W.; Voth, Gregory A.

doi:10.1016/s0301-0104(00)00071-9

Cited by 44 publications

(69 citation statements)

References 48 publications

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“…The implementation of this kind of methodology to study chemical reactivity has been described extensively in the literature [11,12,15,[36][37][38][39][40][41][42][43][44][45][46][47][48]. For such reason, here we will restrict ourselves to introduce only to the main features of the method, following the ideas outlined in Ref.…”

Section: Methodsmentioning

confidence: 99%

Dynamical aspects of intermolecular proton transfer in liquid water and low-density amorphous ices

Tahat

Martı́

2014

Phys. Rev. E

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The microscopic dynamics of an excess proton in water and in low-density amorphous ices has been studied by means of a series of molecular dynamics simulations. Interaction of water with the proton species was modelled using a multistate empirical valence bond Hamiltonian model. The analysis of the effects of low temperatures on proton diffusion and transfer rates has been considered for a temperature range between 100 and 298 K at the constant density of 1 g cm −3 . We observed a marked slowdown of proton transfer rates at low temperatures, but some episodes are still seen at 100 K. In a similar fashion, mobility of the lone proton gets significantly reduced when temperature decreases below 273 K. The proton transfer in low-density amorphous ice is an activated process with energy barriers between 1-10 kJ/mol depending of the temperature range considered and eventually showing Arrhenius-like behavior. Spectroscopic data indicated the survival of both Zundel and Eigen structures along the whole temperature range, revealed by significant spectral frequency shifts.

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Section: Methodsmentioning

confidence: 99%

Dynamical aspects of intermolecular proton transfer in liquid water and low-density amorphous ices

Tahat

Martı́

2014

Phys. Rev. E

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“…empirical states. The MS-EVB approach, based on Warshel's earlier empirical valence bond (EVB) theory [14], is now widely used to simulate the dynamics of excess protons in liquid water [15], through confined single-file water chains [16] and in biological systems [17]. The current limitations of this method involve the lack of an accurate, reactive hydroxide and the nontrivial setup for novice users.…”

Section: Introductionmentioning

confidence: 99%

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

et al. 2011

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Proton transfer to and from water is critical to the function of water in many settings. However, it has been challenging to model. Here, we present proof-of-principle for an efficient yet robust model based on Lewis-inspired submolecular particles with interactions that deviate from Coulombic at short distances to take quantum effects into account. This "LEWIS" model provides excellent correspondence with experimental structures for water molecules and water clusters in their neutral, protonated and deprotonated forms, reasonable values for the proton affinities of water and hydroxide, a good value for the strength of the hydrogen bond in the water dimer, the correct order of magnitude for the stretch and bend force constants of water, and the expected time course for Grotthuss transport in water chains.

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“…The implementation of such kind of methodology has been widely described in the literature [44][45][46][47][48][49][50][51][52][53][54][55][56][57][58], so that here I will restrict myself to give a fair but schematic description of the main features of the method. Full details can be found in a previous work [43] and in references therein.…”

Section: Methodsmentioning

confidence: 99%

“…In the framework of EVB methods, off-diagonal elements h ij can be casted out in terms of nuclear coordinates, achieving an excellent agreement with results from full quantum calculations. The parameterization employed in this work follows was proposed by Schmitt, Voth et al and it has been proven to be very successful in a wide variety of cases [51][52][53][54][55]. The newest version of this procedure (MS-EVB 3.2) was recently published [58] and also inside the rest of water molecules, which are modeled using a flexible TIP3P force field [59].…”

Section: Methodsmentioning

confidence: 99%

Potentials of mean force in acidic proton transfer reactions in constrained geometries

Rabassa

2016

Molecular Simulation

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Free energy barriers associated to the transfer of an excess proton in water and related to the potentials of mean force in proton transfer episodes have been computed in a wide range of thermodynamic states, from low density amorphous ices to high temperature liquids under the critical point for unconstrained and constrained systems. The latter were represented by setups placed inside hydrophobic graphene slabs at the nanometric scale allocating a few water layers, namely one or two in the narrowest case. Waterproton and carbon-proton forces were modelled with a Multi-State Empirical Valence Bond method. As a general trend, a competition between the effects of confinement and temperature is observed on the local hydrogen-bonded structures around the lone proton and, consequently, on the mean force exerted by its environment on the water molecule carrying the proton. Free energy barriers estimated from the computed potentials of mean force tend to rise with the combined effect of increasing temperatures and the packing effect due to a larger extent of hydrophobic confinement. The main reason observed for such enhancement of the free energy barriers was the breaking of the second coordination shell around the lone proton.

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A multi-state empirical valence bond model for acid–base chemistry in aqueous solution

Cited by 44 publications

References 48 publications

Dynamical aspects of intermolecular proton transfer in liquid water and low-density amorphous ices

Dynamical aspects of intermolecular proton transfer in liquid water and low-density amorphous ices

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

Potentials of mean force in acidic proton transfer reactions in constrained geometries

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