Why many semiempirical molecular orbital theories fail for liquid water and how to fix them

Journal of Computational Chemistry
Matthew WelbornTroy Van Voorhis

Abstract

Water is an extremely important liquid for chemistry and the search for more accurate force fields for liquid water continues unabated. Neglect of diatomic differential overlap (NDDO) molecular orbital methods provide and intriguing generalization of classical force fields in this regard because they can account both for bond breaking and electronic polarization of molecules. However, we show that most standard NDDO methods fail for water because they give an incorrect description of hydrogen bonding, water's key structural feature. Using force matching, we design a reparameterized NDDO model and find that it qualitatively reproduces the experimental radial distribution function of water, as well as various monomer, dimer, and bulk properties that PM6 does not. This suggests that the apparent limitations of NDDO models are primarily due to poor parameterization and not to the NDDO approximations themselves. Finally, we identify the physical parameters that most influence the condensed phase properties. These results help to elucidate the chemistry that a semiempirical molecular orbital picture of water must capture. We conclude that properly parameterized NDDO models could be useful for simulations that require electronically d...Continue Reading

References

Mar 1, 1990·Journal of Computer-aided Molecular Design·J J Stewart
Mar 1, 1985·Physical Review A: General Physics·W G Hoover
Jan 11, 2005·The Journal of Chemical Physics·Joost VandeVondeleMichele Parrinello
May 5, 2005·Proceedings of the National Academy of Sciences of the United States of America·William L Jorgensen, Julian Tirado-Rives
Jan 6, 2006·The Journal of Chemical Physics·J L F Abascal, C Vega
Aug 12, 2006·Physical Chemistry Chemical Physics : PCCP·Yihan ShaoMartin Head-Gordon
May 5, 2007·The Journal of Chemical Physics·Hee-Seung Lee, Mark E Tuckerman
Mar 21, 2008·Nature·Philip Ball
Jun 12, 2013·The Journal of Physical Chemistry. B·Lee-Ping WangVijay S Pande
Feb 12, 2014·The Journal of Chemical Physics·Erich R Kuechler, Darrin M York
Jul 24, 2014·The Journal of Chemical Physics·Antoine MarionFrancesca Ingrosso
Mar 1, 2008·Journal of Chemical Theory and Computation·Berk HessErik Lindahl
Nov 1, 2007·Journal of Chemical Theory and Computation·Arieh WarshelAndrei V Pisliakov

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Citations

Nov 18, 2015·Journal of Chemical Theory and Computation·Nir GoldmanLucas Koziol
Jun 15, 2016·The Journal of Physical Chemistry. a·Maxim Tafipolsky
Dec 23, 2016·Journal of Chemical Theory and Computation·Lucas KoziolNir Goldman
Nov 2, 2021·Journal of Chemical Theory and Computation·Bryant KimJingzhi Pu

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