Determining polarizable force fields with electrostatic potentials from quantum mechanical linear response theory

Wang, Hao; Yang, Weitao

doi:10.1063/1.4953558

Cited by 12 publications

(17 citation statements)

References 60 publications

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“…(125) Wang et al developed a method to calculate the atomic polarizabilities by fitting to the electrostatic potentials (ESPs) under external electric field obtained from quantum mechanical (QM) calculations within the linear response theory. (129) The molecular polarizability obtained from this method is comparable to those from directly fitting to molecular polarizabilities. For polar molecules such as water, polarization is highly anisotropic.…”

Section: Atomic Polarizabilitymentioning

confidence: 71%

Polarizable Force Fields for Biomolecular Simulations: Recent Advances and Applications

Jing

Liu

Cheng

et al. 2019

Annu. Rev. Biophys.

341

352

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Realistic modeling of biomolecular systems requires an accurate treatment of electrostatics, including electronic polarization. Due to recent advances in physical models, simulation algorithms, and computing hardware, biomolecular simulations with advanced force fields at biologically relevant timescales are becoming increasingly promising. These advancements have not only led to new biophysical insights but also afforded opportunities to advance our understanding of fundamental intermolecular forces. This article describes the recent advances and applications, as well as future directions, of polarizable force fields in biomolecular simulations.

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Section: Atomic Polarizabilitymentioning

confidence: 71%

Polarizable Force Fields for Biomolecular Simulations: Recent Advances and Applications

Jing

Liu

Cheng

et al. 2019

Annu. Rev. Biophys.

341

352

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“…This is comparable to the atomic polarizability for sp 3 oxygen in the range of 2.88 to 5.21 in Table 1 in the recent paper from Wang and Yang. 50 …”

Section: Resultsmentioning

confidence: 99%

“…Overall, these atomic polarizability values are slightly higher than the values of 5.00-9.13 for sp 3 carbon atoms and 4.51–13.40 for sp 2 carbon atoms as reported by Wang and Yang. 50 …”

Section: Resultsmentioning

confidence: 99%

“…Similar response kernels were also used in Atom-Condensed Kohn-Sham Density Functional Theory approximated to second order (ACKS2) by Verstraelen, Vandenbrande, and Ayers 49 , and in the fitting of atomic polarizabilities for polarizable force fields by Wang and Yang 50 . The second key component of our framework is to approximate the electrostatic potential of each occupied-virtual molecular orbital pair in two different ways: (a) as a potential of atomic charges (PAC); or (b) as a potential of atomic dipoles (PAD), where all charges or dipoles are located on QM atomic sites.…”

Section: Introductionmentioning

confidence: 99%

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An Estimation of Hybrid Quantum Mechanical Molecular Mechanical Polarization Energies for Small Molecules Using Polarizable Force-Field Approaches

Huang

König

et al. 2017

J. Chem. Theory Comput.

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In this work, we report two polarizable molecular mechanics (polMM) force field models for estimating the polarization energy in hybrid quantum mechanical molecular mechanical (QM/MM) calculations. These two models, named the potential of atomic charges (PAC) and potential of atomic dipoles (PAD), are formulated from the ab initio quantum mechanical (QM) response kernels for the prediction of the QM density response to an external molecular mechanical (MM) environment (as described by external point charges). The PAC model is similar to fluctuating charge (FQ) models because the energy depends on external electrostatic potential values at QM atomic sites; the PAD energy depends on external electrostatic field values at QM atomic sites, resembling induced dipole (ID) models. To demonstrate their uses, we apply the PAC and PAD models to twelve small molecules, which are solvated by TIP3P water. The PAC model reproduces the QM/MM polarization energy with a R2 value of 0.71 for aniline (in 10,000 TIP3P water configurations) and 0.87 or higher for other eleven solute molecules, while the PAD model has a much better performance with R2 values of 0.98 or higher. The PAC model reproduces reference QM/MM hydration free energies for twelve solute molecules with a RMSD of 0.59 kcal/mol. The PAD model is even more accurate, with a much smaller RMSD of 0.12 kcal/mol, with respect to the reference. This suggests that polarization effects, including both local charge distortion and intramolecular charge transfer, can be well captured by induced dipole type models with proper parameterization.

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“…The similarity between the classical Drude oscillator model and the induced point dipole model has often been speculated. [74][75][76][77] Here we quantify their similarity using an extensive set of molecules with realistic polarizable force field parameters. The fact that the Drude FF can be directly converted into MPID without any reparametrization illustrates that the Drude oscillator model and the induced dipole model are different representations of the same physical model for including electronic polarization.…”

Section: Discussionmentioning

confidence: 99%

Mapping the Drude polarizable force field onto a multipole and induced dipole model

Huang

Simmonett

Pickard

et al. 2017

The Journal of Chemical Physics

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The induced dipole and the classical Drude oscillator represent two major approaches for the explicit inclusion of electronic polarizability into force field-based molecular modeling and simulations. In this work, we explore the equivalency of these two models by comparing condensed phase properties computed using the Drude force field and a multipole and induced dipole (MPID) model. Presented is an approach to map the electrostatic model optimized in the context of the Drude force field onto the MPID model. Condensed phase simulations on water and 15 small model compounds show that without any reparametrization, the MPID model yields properties similar to the Drude force field with both models yielding satisfactory reproduction of a range of experimental values and quantum mechanical data. Our results illustrate that the Drude oscillator model and the point induced dipole model are different representations of essentially the same physical model. However, results indicate the presence of small differences between the use of atomic multipoles and off-center charge sites. Additionally, results on the use of dispersion particle mesh Ewald further support its utility for treating long-range Lennard Jones dispersion contributions in the context of polarizable force fields. The main motivation in demonstrating the transferability of parameters between the Drude and MPID models is that the more than 15 years of development of the Drude polarizable force field can now be used with MPID formalism without the need for dual-thermostat integrators nor self-consistent iterations. This opens up a wide range of new methodological opportunities for polarizable models.

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Determining polarizable force fields with electrostatic potentials from quantum mechanical linear response theory

Cited by 12 publications

References 60 publications

Polarizable Force Fields for Biomolecular Simulations: Recent Advances and Applications

Polarizable Force Fields for Biomolecular Simulations: Recent Advances and Applications

An Estimation of Hybrid Quantum Mechanical Molecular Mechanical Polarization Energies for Small Molecules Using Polarizable Force-Field Approaches

Mapping the Drude polarizable force field onto a multipole and induced dipole model

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