A Hirshfeld partitioning of polarizabilities of water clusters

Krishtal, Alisa; Senet, Patrick; Yang, Mingli; Alsenoy, C. Van

doi:10.1063/1.2210937

Cited by 76 publications

(124 citation statements)

References 54 publications

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“…Numerous studies have demonstrated the difference in molecular polarizability between molecules in the gas and condensed phases. [49][50][51] The TIP4P-QDP model of Bauer et al 52 introduces phase-dependent polarizability into a classical simulation. The electrostatic component of the Hamiltonian is modified such that the and parameters are functions of the M-site ͑lone-pair site͒ charge,…”

Section: B Phase-dependent Polarizable Modelmentioning

confidence: 99%

“…[49][50][51] Generally accepted reductions fall either in the range of 7%-10% or 30%. Using the Hirshfeld partitioning scheme and density functional theory calculations, Krishtal et al 50 explored the dependence of polarizability on water cluster size. They reported that the intrinsic molecular polarizability decreases with increasing cluster size, converging to a bulklike value in the limit of a significantly large cluster ͑n H 2 O =20͒.…”

Section: Introductionmentioning

confidence: 99%

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Molecular dynamics simulations of nonpolarizable inorganic salt solution interfaces: NaCl, NaBr, and NaI in transferable intermolecular potential 4-point with charge dependent polarizability (TIP4P-QDP) water

Bauer

Patel

2010

The Journal of Chemical Physics

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We present molecular dynamics simulations of the liquid-vapor interface of 1M salt solutions of nonpolarizable NaCl, NaBr, and NaI in polarizable transferable intermolecular potential 4-point with charge dependent polarizability water ͓B. A. Bauer et al., J. Chem. Theory Comput. 5, 359 ͑2009͔͒; this water model accommodates increased solvent polarizability ͑relative to the condensed phase͒ in the interfacial and vapor regions. We employ fixed-charge ion models developed in conjunction with the TIP4P-QDP water model to reproduce ab initio ion-water binding energies and ion-water distances for isolated ion-water pairs. The transferability of these ion models to the condensed phase was validated with hydration free energies computed using thermodynamic integration ͑TI͒ and appropriate energy corrections. Density profiles of Cl − , Br − , and I − exhibit charge layering in the interfacial region; anions and cation interfacial probabilities show marked localization, with the anions penetrating further toward the vapor than the cations. Importantly, in none of the cases studied do anions favor the outermost regions of the interface; there is always an aqueous region between the anions and vapor phase. Observed interfacial charge layering is independent of the strength of anion-cation interactions as manifest in anion-cation contact ion pair peaks and solvent separated ion pair peaks; by artificially modulating the strength of anion-cation interactions ͑independent of their interactions with solvent͒, we find little dependence on charge layering particularly for the larger iodide anion. The present results reiterate the widely held view of the importance of solvent and ion polarizability in mediating specific anion surface segregation effects. Moreover, due to the higher parametrized polarizability of the TIP4P-QDP condensed phase ͕1.31 Å 3 for TIP4P-QDP versus 1.1 Å 3 ͑TIP4P-FQ͒ and 0.87 Å 3 ͑POL3͒ ͓Ponder and Case, Adv. Protein Chem. 66, 27 ͑2003͔͖͒ based on ab initio calculations of the condensed-phase polarizability reduction in liquid water, the present simulations highlight the role of water polarizability in inducing water molecular dipole moments parallel to the interface normal ͑and within the interfacial region͒ so as to favorably oppose the macrodipole generated by the separation of anion and cation charge. Since the TIP4P-QDP water polarizability approaches that of the experimental vapor phase value for water, the present results suggest a fundamental role of solvent polarizability in accommodating the large spatial dipole generated by the separation of ion charges. The present results draw further attention to the question of what exact value of condensed phase water polarizability to incorporate in classical polarizable water force fields.

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Section: B Phase-dependent Polarizable Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Molecular dynamics simulations of nonpolarizable inorganic salt solution interfaces: NaCl, NaBr, and NaI in transferable intermolecular potential 4-point with charge dependent polarizability (TIP4P-QDP) water

Bauer

Patel

2010

The Journal of Chemical Physics

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“…31 Recently, the fuzzy Hirshfeld partitioning scheme of the electron density has also been applied to extract molecular polarizabilities in clusters 32,33 or atomic polarizabilities in large molecular systems. 9 However, a disadvantage of the Hirshfeld scheme, at least in the current implementations, is that the functional-group polarizabilities remain origin-dependent and, therefore, cannot be properly exported to other systems.…”

Section: Introductionmentioning

confidence: 99%

Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates

2015

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With the purpose of rational design of optical materials, distributed atomic polarizabilities of amino acid molecules and their hydrogen-bonded aggregates are calculated in order to identify the most efficient functional groups, able to buildup larger electric susceptibilities in crystals.Moreover, we carefully analyze how the atomic polarizabilities depend on the one-electron basis set or the many-electron Hamiltonian, including both wave function and density functional theory methods. This is useful for selecting the level of theory that best combines high accuracy and low computational costs, very important in particular when using the cluster method to estimate susceptibilities of molecular-based materials.KEYWORDS: distributed polarizability, quantum theory of atoms in molecules, electron density distribution, linear optical properties, hydrogen bonding.2

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“…36 It is especially encouraging that the SQE model exhibits a transition between the EEM-like polarizability scaling for small systems to the linear scaling for extended systems, 34,36 as is often observed in computational studies. 13,[37][38][39][40] Since the primary goal of all CPE-based models is the fast and reliable computation of charge distribution in large systems, the parameterization of such a model is done by fitting atomic charges produced by the model to those derived from quantum-chemical calculations. The problem is that the atomic charge is not a quantum-chemical observable 41 and consequently, many electronic density partitioning schemes can be used to produce the reference charge values.…”

Section: Introductionmentioning

confidence: 99%

Computation of Charge Distribution and Electrostatic Potential in Silicates with the Use of Chemical Potential Equalization Models

et al. 2011

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New parameters for the electronegativity equalization model (EEM) and the split-charge equilibration (SQE) model are calibrated for silicate materials, based on an extensive training set of representative isolated systems. In total, four calibrations are carried out, two for each model, either using iterative Hirshfeld (HI) charges or ESP grid data computed with Density Functional Theory (DFT) as a reference. Both the static (ground state) reference quantities and their responses to uniform electric fields are included in the fitting procedure. The EEM model fails to describe the response data, while the SQE model quantitatively reproduces all the training data. For the ESP-based parameters, we found that the reference ESP data are only useful at those grid points where the electron density is lower than 10 −3 a.u. The density value correlates with a distance criterion used for selecting grid points in common ESP fitting schemes.All parameters are validated with DFT computations on an independent set of isolated systems (similar to the training set), and on a set of periodic systems including dense and microporous crystalline silica structures, zirconia, and zirconium silicate. Although the transferability of the parameters to new isolated systems poses no difficulties, the atomic hardness parameters in the HI-based models must be corrected to obtain accurate results for periodic systems. The SQE/ESP model permits the calculation of the ESP with similar accuracy in both isolated and periodic systems.

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A Hirshfeld partitioning of polarizabilities of water clusters

Cited by 76 publications

References 54 publications

Molecular dynamics simulations of nonpolarizable inorganic salt solution interfaces: NaCl, NaBr, and NaI in transferable intermolecular potential 4-point with charge dependent polarizability (TIP4P-QDP) water

Molecular dynamics simulations of nonpolarizable inorganic salt solution interfaces: NaCl, NaBr, and NaI in transferable intermolecular potential 4-point with charge dependent polarizability (TIP4P-QDP) water

Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates

Computation of Charge Distribution and Electrostatic Potential in Silicates with the Use of Chemical Potential Equalization Models

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