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Flexible-boundary QM/MM calculations: II. Partial charge transfer across the QM/MM boundary that passes through a covalent bond

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Abstract

Recently, based on the principle of electronic chemical potential equalization and the principle of charge conservation, we proposed a flexible-boundary scheme that allows both partial charge transfer and self-consistent polarization between the quantum mechanical (QM) and molecular mechanical (MM) subsystems in QM/MM calculations; the scheme was applied to study the atomic charges in selected ion–solvent complexes. In the present contribution, we further extend the flexible-boundary treatment to handle the QM/MM boundary passing through covalent bonds. We find that the flexible-boundary redistributed charge and dipole schemes yield reasonable agreement with full-QM calculations for a number of molecular ions and amino acids with charged side chains. Using the full-QM results as reference, the mean unsigned deviations are computed to be 0.06 e for atomic partial charges of the QM atoms, 0.11 e for the amounts of charge transfer between the QM and MM subsystems, and 0.016 Å for the lengths of the covalent bonds that directly connect the QM and MM subsystems. The results indicate the importance of accounting for partial charge transfer across the QM/MM boundary when the QM subsystems are charged.

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Acknowledgments

This work is supported by the Research Corporation. We thank the National Cancer Institute-Frederick Advanced Biomedical Computing Center and the Minnesota Supercomputing Institute for providing CPU time and access to the Gaussian03 program.

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  1. Chemistry Department, University of Colorado Denver, Denver, CO, 80210-3364, USA

    Yan Zhang & Hai Lin

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  1. Yan Zhang
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  2. Hai Lin
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Correspondence to Hai Lin.

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Zhang, Y., Lin, H. Flexible-boundary QM/MM calculations: II. Partial charge transfer across the QM/MM boundary that passes through a covalent bond. Theor Chem Acc 126, 315–322 (2010). https://doi.org/10.1007/s00214-009-0704-z

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