Erratum to ‘QTPIE: Charge transfer with polarization current equalization. A fluctuating charge model with correct asymptotics’ [Chem. Phys. Lett. 438 (2007) 315]

Chen, Jiahao; ́nez, Todd J. Martı

doi:10.1016/j.cplett.2008.08.060

Cited by 41 publications

(91 citation statements)

References 2 publications

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“…͑9͔͒, the BR will be rank deficient for all but the minimum number of BCVs and will contain zero eigenvalues. 15 This problem may be avoided by performing a singular value decomposition 2,15 or by restricting the charge transfer topology a priori which is the approach used in the present work. The BR of the atomic QEq method, which we will refer to as the QE scheme, may be constructed from Eqs.…”

Section: B Bond Representationsmentioning

confidence: 99%

“…By exploiting the antisymmetry of the BCVs ͑q ij =−q ji ͒ and letting J ii = i 0 , this expression may be recast 2,15 in the form…”

Section: B Bond Representationsmentioning

confidence: 99%

“…Thus, a "bond" in this formalism does not necessarily represent a literal chemical bond, but rather the capacity for two atoms to engage in charge transfer; however, in many instances there exists a one-to-one correspondence between BR bonds and actual chemical bonds. A wide variety of nomenclatures for these BR variables exist including bond charge increments, 2,3 atom-atom charges, 5 charge transfer variables, 15 and split charges. 17 For the sake of consistency and clarity throughout, we will refer to the variables in AR schemes as atomic charge variables and those corresponding to BR schemes as bond charge variables ͑BCVs͒ where the labels "atomic" and "bond" signify one-body ͑singly indexed͒ and two-body ͑doubly indexed͒ charge variables, respectively.…”

Section: B Bond Representationsmentioning

confidence: 99%

“…Given the ongoing refinement and development of Eq methods, such as those incorporating distance-dependent charge transfer, 15 it is timely to precisely characterize the specific origins of this scaling problem so that it may be systematically controlled in all future models.…”

Section: Introductionmentioning

confidence: 99%

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Origin and control of superlinear polarizability scaling in chemical potential equalization methods

Warren

Davis²,

Patel³

2008

The Journal of Chemical Physics

154

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Many common chemical potential equalization ͑ Eq͒ methods are known to suffer from a superlinear scaling of the polarizability with increasing molecular size that interferes with model transferability and prevents the straightforward application of these methods to large, biochemically relevant molecules. In the present work, we systematically investigate the origins of this scaling and the mechanisms whereby some existing methods successfully temper the scaling. We demonstrate several types of topological charge constraints distinct from the usual single molecular charge constraint that can successfully achieve linear polarizability scaling in atomic charge based equilibration models. We find the use of recently employed charge conservation constraints tied to small molecular units to be an effective and practical approach for modulating the polarizability scaling in atomic Eq schemes. We also analyze the scaling behavior of several Eq schemes in the bond representation and derive closed-form expressions for the polarizability scaling in a linear atomic chain model; for a single molecular charge constraint these expressions demonstrate a cubic dependence of the polarizability on molecular size compared with linear scaling obtainable in the case of the atom-atom charge transfer ͑AACT͒ and split-charge equilibration ͑SQE͒ schemes. Application of our results to the trans N-alkane series reveals that in certain situations, the AACT and SQE schemes can become unstable due to an indefinite Hessian matrix. Consequently, we discuss sufficient criteria for ensuring stability within these schemes.

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Section: B Bond Representationsmentioning

confidence: 99%

“…By exploiting the antisymmetry of the BCVs ͑q ij =−q ji ͒ and letting J ii = i 0 , this expression may be recast 2,15 in the form…”

Section: B Bond Representationsmentioning

confidence: 99%

Section: B Bond Representationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Origin and control of superlinear polarizability scaling in chemical potential equalization methods

Warren

Davis²,

Patel³

2008

The Journal of Chemical Physics

154

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“…61 In addition, these classical models do not account for charge transfer; force fields to handle charge transfer are under active development. 62, 63 Wick 60 has recently shown that increased local damping of the charged interactions during the polarization self-consistency step, leading to smaller anion dipoles, reduces the surface affinity of anions at the water liquid-vapor interface.…”

Section: B Ion and Water Dipole Moments And Charge Transfermentioning

confidence: 99%

Polarization and charge transfer in the hydration of chloride ions

Zhao

Rogers

Beck

2010

The Journal of Chemical Physics

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A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation, and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The Quantum Theory of Atoms in Molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared with the estimated quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2 level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

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Reactive Force Fields: Concepts of ReaxFF

Duin

2009

Computational Methods in Catalysis and Materials Science

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Erratum to ‘QTPIE: Charge transfer with polarization current equalization. A fluctuating charge model with correct asymptotics’ [Chem. Phys. Lett. 438 (2007) 315]

Cited by 41 publications

References 2 publications

Origin and control of superlinear polarizability scaling in chemical potential equalization methods

Origin and control of superlinear polarizability scaling in chemical potential equalization methods

Polarization and charge transfer in the hydration of chloride ions

Reactive Force Fields: Concepts of ReaxFF

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