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Journal of Chemical Physics / Volume 129 / Issue 14 / ARTICLES / Biological Molecules, Biopolymers, and Biological Systems

J. Chem. Phys. 129, 145101 (2008); http://dx.doi.org/10.1063/1.2976570 (10 pages)

Applications and assessment of QM:QM electronic embedding using generalized asymmetric Mulliken atomic charges

Priya V. Parandekar, Hrant P. Hratchian, and Krishnan Raghavachari

Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA

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(Received 13 May 2008; accepted 6 August 2008; published online 10 October 2008)

Hybrid QM:QM (quantum mechanics:quantum mechanics) and QM:MM (quantum mechanics:molecular mechanics) methods are widely used to calculate the electronic structure of large systems where a full quantum mechanical treatment at a desired high level of theory is computationally prohibitive. The ONIOM (our own N-layer integrated molecular orbital molecular mechanics) approximation is one of the more popular hybrid methods, where the total molecular system is divided into multiple layers, each treated at a different level of theory. In a previous publication, we developed a novel QM:QM electronic embedding scheme within the ONIOM framework, where the model system is embedded in the external Mulliken point charges of the surrounding low-level region to account for the polarization of the model system wave function. Therein, we derived and implemented a rigorous expression for the embedding energy as well as analytic gradients that depend on the derivatives of the external Mulliken point charges. In this work, we demonstrate the applicability of our QM:QM method with point charge embedding and assess its accuracy. We study two challenging systems—zinc metalloenzymes and silicon oxide cages—and demonstrate that electronic embedding shows significant improvement over mechanical embedding. We also develop a modified technique for the energy and analytic gradients using a generalized asymmetric Mulliken embedding method involving an unequal splitting of the Mulliken overlap populations to offer improvement in situations where the Mulliken charges may be deficient.

© 2008 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. METHODS
    1. Generalized asymmetric Mulliken embedding (GAME): Energy and gradients
  3. ASSESSMENT OF THE ONIOM-QM:QM MULLIKEN POINT CHARGE EMBEDDING SCHEME
  4. CONCLUSIONS

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KEYWORDS and PACS

Keywords

macromolecules, orbital calculations, organometallic compounds, quantum chemistry, silicon compounds

PACS

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2976570

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    V. Gogonea, L. M. Westerhoff, and K. M. Merz, J. Chem. Phys. 113, 5604 (2000)JCPSA6000113000014005604000001.

    H. P. Hratchian, P. V. Parandekar, K. Raghavachari, M. J. Frisch, and T. Vreven, J. Chem. Phys. 128, 034107 (2008)JCPSA6000128000003034107000001.

    N. C. Handy and H. F. Schaefer III, J. Chem. Phys. 81, 5031 (1984)JCPSA6000081000011005031000001.

    R. S. Mulliken, J. Chem. Phys. 23, 1833 (1955)JCPSA6000023000010001833000001.

    A. Ruzsinszky and J. P. Perdew, J. Chem. Phys. 125, 194112 (2006)JCPSA6000125000019194112000001.


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