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Performance of the AMOEBA water model in the vicinity of QM solutes: a diagnosis using energy decomposition analysis

Performance of the AMOEBA water model in the vicinity of QM solutes: a diagnosis using energy decomposition analysis
Performance of the AMOEBA water model in the vicinity of QM solutes: a diagnosis using energy decomposition analysis
The importance of incorporating solvent polarization effects into the modeling of solvation processes has been well-recognized, and therefore a new generation of hybrid quantum mechanics/molecular mechanics (QM/MM) approaches that accounts for this effect is desirable. We present a fully self-consistent, mutually polarizable QM/MM scheme using the AMOEBA force field, in which the total energy of the system is variationally minimized with respect to both the QM electronic density and the MM induced dipoles. This QM/AMOEBA model is implemented through the Q-Chem/LibEFP code interface and then applied to the evaluation of solute–solvent interaction energies for various systems ranging from the water dimer to neutral and ionic solutes (NH3, NH4+, CN–) surrounded by increasing numbers of water molecules (up to 100). In order to analyze the resulting interaction energies, we also utilize an energy decomposition analysis (EDA) scheme which identifies contributions from permanent electrostatics, polarization, and van der Waals (vdW) interaction for the interaction between the QM solute and the solvent molecules described by AMOEBA. This facilitates a component-wise comparison against full QM calculations where the corresponding energy components are obtained via a modified version of the absolutely localized molecular orbitals (ALMO)-EDA. The results show that the present QM/AMOEBA model can yield reasonable solute–solvent interaction energies for neutral and cationic species, while further scrutiny reveals that this accuracy highly relies on the delicate balance between insufficiently favorable permanent electrostatics and softened vdW interaction. For anionic solutes where the charge penetration effect becomes more pronounced, the QM/MM interface turns out to be unbalanced. These results are consistent with and further elucidate our findings in a previous study using a slightly different QM/AMOEBA model (Dziedzic et al. J. Chem. Phys. 2016, 145, 124106). The implications of these results for further refinement of this model are also discussed.
1549-9618
1963-1979
Mao, Yuezhi
19117f2e-bd57-431d-ad0e-f36f4aa2187c
Shao, Yihan
6b0b8a41-eacf-4359-b7b1-79058fecbc81
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Head-Gordon, Teresa
11febdf4-20fa-4abb-97a1-3305c6e81b09
Head-Gordon, Martin
f203c934-60ff-4c19-a2ff-b1f6ec2ad05a
Mao, Yuezhi
19117f2e-bd57-431d-ad0e-f36f4aa2187c
Shao, Yihan
6b0b8a41-eacf-4359-b7b1-79058fecbc81
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Head-Gordon, Teresa
11febdf4-20fa-4abb-97a1-3305c6e81b09
Head-Gordon, Martin
f203c934-60ff-4c19-a2ff-b1f6ec2ad05a

Mao, Yuezhi, Shao, Yihan, Dziedzic, Jacek, Skylaris, Chris-Kriton, Head-Gordon, Teresa and Head-Gordon, Martin (2017) Performance of the AMOEBA water model in the vicinity of QM solutes: a diagnosis using energy decomposition analysis. Journal of Chemical Theory and Computation, 13 (5), 1963-1979. (doi:10.1021/acs.jctc.7b00089).

Record type: Article

Abstract

The importance of incorporating solvent polarization effects into the modeling of solvation processes has been well-recognized, and therefore a new generation of hybrid quantum mechanics/molecular mechanics (QM/MM) approaches that accounts for this effect is desirable. We present a fully self-consistent, mutually polarizable QM/MM scheme using the AMOEBA force field, in which the total energy of the system is variationally minimized with respect to both the QM electronic density and the MM induced dipoles. This QM/AMOEBA model is implemented through the Q-Chem/LibEFP code interface and then applied to the evaluation of solute–solvent interaction energies for various systems ranging from the water dimer to neutral and ionic solutes (NH3, NH4+, CN–) surrounded by increasing numbers of water molecules (up to 100). In order to analyze the resulting interaction energies, we also utilize an energy decomposition analysis (EDA) scheme which identifies contributions from permanent electrostatics, polarization, and van der Waals (vdW) interaction for the interaction between the QM solute and the solvent molecules described by AMOEBA. This facilitates a component-wise comparison against full QM calculations where the corresponding energy components are obtained via a modified version of the absolutely localized molecular orbitals (ALMO)-EDA. The results show that the present QM/AMOEBA model can yield reasonable solute–solvent interaction energies for neutral and cationic species, while further scrutiny reveals that this accuracy highly relies on the delicate balance between insufficiently favorable permanent electrostatics and softened vdW interaction. For anionic solutes where the charge penetration effect becomes more pronounced, the QM/MM interface turns out to be unbalanced. These results are consistent with and further elucidate our findings in a previous study using a slightly different QM/AMOEBA model (Dziedzic et al. J. Chem. Phys. 2016, 145, 124106). The implications of these results for further refinement of this model are also discussed.

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Accepted/In Press date: 21 April 2017
e-pub ahead of print date: 21 April 2017
Organisations: Computational Systems Chemistry

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Local EPrints ID: 410554
URI: http://eprints.soton.ac.uk/id/eprint/410554
ISSN: 1549-9618
PURE UUID: 10a0c9fa-6249-4d59-9e87-e23d245fd5ed
ORCID for Jacek Dziedzic: ORCID iD orcid.org/0000-0003-4786-372X
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 09 Jun 2017 09:05
Last modified: 16 Mar 2024 05:22

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Contributors

Author: Yuezhi Mao
Author: Yihan Shao
Author: Jacek Dziedzic ORCID iD
Author: Teresa Head-Gordon
Author: Martin Head-Gordon

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