Directional dependence of hydrogen bonds: A density-based energy decomposition analysis and its implications on force field development

Zhenyu Lu, Nengjie Zhou, Qin Wu, Yingkai Zhang

Research output: Contribution to journalArticle

Abstract

One well-known shortcoming of widely used biomolecular force fields is the description of the directional dependence of hydrogen bonding (HB). Here we aim to better understand the origin of this difficulty and thus provide some guidance for further force field development. Our theoretical approaches center on a novel density-based energy decomposition analysis (DEDA) method (J. Chem. Phys. 2009, 131, 164112), in which the frozen density energy is variationally determined through constrained search. This unique and most significant feature of DEDA enables us to find that the frozen density interaction term is the key factor in determining the HB orientation, while the sum of polarization and charge-transfer components shows very little HB directional dependence. This new insight suggests that the difficulty for current nonpolarizable force fields to describe the HB directional dependence is not due to the lack of explicit polarization or charge-transfer terms. Using the DEDA results as reference, we further demonstrate that the main failure coming from the atomic point charge model can be overcome largely by introducing extra charge sites or higher order multipole moments. Among all the electrostatic models explored, the smeared charge distributed multipole model (up to quadrupole), which also takes account of charge penetration effects, gives the best agreement with the corresponding DEDA results. Meanwhile, our results indicate that the van der Waals interaction term needs to be further improved to better model directional HB.

Original languageEnglish (US)
Pages (from-to)4038-4049
Number of pages12
JournalJournal of Chemical Theory and Computation
Volume7
Issue number12
DOIs
StatePublished - Dec 13 2011

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field theory (physics)
Hydrogen bonds
hydrogen bonds
Decomposition
decomposition
hydrogen
multipoles
Charge transfer
charge transfer
energy
Polarization
polarization
Electrostatics
penetration
flux density
quadrupoles
interactions
electrostatics
moments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

Directional dependence of hydrogen bonds : A density-based energy decomposition analysis and its implications on force field development. / Lu, Zhenyu; Zhou, Nengjie; Wu, Qin; Zhang, Yingkai.

In: Journal of Chemical Theory and Computation, Vol. 7, No. 12, 13.12.2011, p. 4038-4049.

Research output: Contribution to journalArticle

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