Reptation Quantum Monte Carlo calculation of charge transfer: The Na–Cl dimer

Yao, Yi; Kanai, Yosuke

doi:10.1016/j.cplett.2014.10.002

Cited by 4 publications

(2 citation statements)

References 57 publications

(68 reference statements)

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“…In order to put into perspective our results for Na–Cl in water using the SCAN and ωB97X-V functionals, we first discuss how different XC approximations perform for the potential energy curve for NaCl dissociation in vacuum . MP2 calculation is used as the reference, and the same basis set is used for all calculations (see the Supporting Informaiton for comparison between MP2 and CCSD(T) calculations).…”

Section: Resultsmentioning

confidence: 99%

Free Energy Profile of NaCl in Water: First-Principles Molecular Dynamics with SCAN and ωB97X-V Exchange–Correlation Functionals

Yao

Kanai

2018

J. Chem. Theory Comput.

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Properties of water and aqueous ionic solutions are of great scientific interest because they play a central role in the atmosphere, biological environments, and various industrial processes. Employing two advanced exchange-correlation (XC) approximations, ωB97X-V and SCAN, in first-principles molecular dynamics simulations, we calculate the potential of mean force of NaCl in water as a function of the ion separation distance. Compared to the commonly used GGA-PBE functional, both of these XC functionals perform much better in simulating liquid water at room temperature for obtaining structural properties. The potential of mean force of NaCl in water exhibits two minima corresponding to two distinct types of ion pairing. ωB97X-V predicts that the contact ion pair is energetically more stable than the solvent-separated ion pair. The SCAN functional, however, predicts the opposite stability order, similarly to other XC functionals such as PBE. This is notable especially since classical molecular dynamics simulations with widely used force-field models predict greater stability for the contact ion pair. We also discuss how the electronic structures of water molecules and ions depend on the XC approximations. ωB97X-V and SCAN approximations noticeably improve the description of electron charge on Cl ion in water while the charge on Na ion does not vary appreciably among the three XC functionals.

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Section: Resultsmentioning

confidence: 99%

Free Energy Profile of NaCl in Water: First-Principles Molecular Dynamics with SCAN and ωB97X-V Exchange–Correlation Functionals

Yao

Kanai

2018

J. Chem. Theory Comput.

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“…Employing the hybrid functional PBE0 [51] and range-corrected hybrid XC functional LC-BLYP [52], we examined differences with the PBE result at v proton = 0.89, 1.90, and 6.27 a.u.. In our recent work, LC-BLYP functional was found to perform quite satisfactorily in describing a long-range charge transfer in comparison to reptation quantum Monte Carlo and coupled cluster calculations [53]. For examining the XC dependence of the electronic stopping power, we used a Gaussian basis set instead of a plane-wave basis due to the prohibitively large computational cost of using plane-wave basis for these hybrid functionals in the present context.…”

Section: Figmentioning

confidence: 99%

Electronic stopping power in liquid water for protons and α particles from first principles

2016

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Atomistic calculations of the electronic stopping power in liquid water for protons and α-particles from first principles are demonstrated without relying on linear response theory. The computational approach is based on non-equilibrium simulation of the electronic response using real-time time-dependent density functional theory. By quantifying the velocity-dependence of the steady-state charge of the projectile proton and αparticle from non-equilibrium electron densities, we examine the extent to which linear response theory is applicable. We further assess the influence of the exchange-correlation approximation in real-time timedependent density functional theory on the stopping power with range-separated and regular hybrid functionals with exact exchange.

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Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

Yao

Berkowitz

Kanai

2015

The Journal of Chemical Physics

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The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na(+) and K(+) ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

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Reptation Quantum Monte Carlo calculation of charge transfer: The Na–Cl dimer

Cited by 4 publications

References 57 publications

Free Energy Profile of NaCl in Water: First-Principles Molecular Dynamics with SCAN and ωB97X-V Exchange–Correlation Functionals

Free Energy Profile of NaCl in Water: First-Principles Molecular Dynamics with SCAN and ωB97X-V Exchange–Correlation Functionals

Electronic stopping power in liquid water for protons and α particles from first principles

Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

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