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Solvent effects on electronic properties from Wannier functions in a dimethyl sulfoxide/water mixture


Kirchner, B; Hutter, J (2004). Solvent effects on electronic properties from Wannier functions in a dimethyl sulfoxide/water mixture. Journal of Chemical Physics, 121(11):5133-5142.

Abstract

We present an efficient implementation for the calculation of maximally localized Wannier functions (MLWFs) during parallel Car-Parrinello molecular dynamics simulations. The implementation is based on a block Jacobi method. The calculation of MLWFs results in only a moderate (10%-20%) increase in computer time. Consequently it is possible to calculate MLWFs routinely during Car-Parrinello simulations. The Wannier functions are then applied to derive molecular dipole moments of dimethyl sulfoxide (DMSO) in gas phase and aqueous solution. We observe a large increase of the local dipole moment from 3.97 to 7.39 D. This large solvent effect is caused by strong hydrogen bonding at the DMSO oxygen atom and methyl groups. Decomposing the dipole moment into local contributions from the S-O bond and the methyl groups is used to understand the electrostatic response of DMSO in aqueous solution. A scheme is given to derive charges on individual atoms from the MLWFs using the D-RESP methodology. The charges also display large solvent effects and give insight into the transferability of recent force field models for DMSO.

We present an efficient implementation for the calculation of maximally localized Wannier functions (MLWFs) during parallel Car-Parrinello molecular dynamics simulations. The implementation is based on a block Jacobi method. The calculation of MLWFs results in only a moderate (10%-20%) increase in computer time. Consequently it is possible to calculate MLWFs routinely during Car-Parrinello simulations. The Wannier functions are then applied to derive molecular dipole moments of dimethyl sulfoxide (DMSO) in gas phase and aqueous solution. We observe a large increase of the local dipole moment from 3.97 to 7.39 D. This large solvent effect is caused by strong hydrogen bonding at the DMSO oxygen atom and methyl groups. Decomposing the dipole moment into local contributions from the S-O bond and the methyl groups is used to understand the electrostatic response of DMSO in aqueous solution. A scheme is given to derive charges on individual atoms from the MLWFs using the D-RESP methodology. The charges also display large solvent effects and give insight into the transferability of recent force field models for DMSO.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2004
Deposited On:26 Mar 2009 21:24
Last Modified:01 Jun 2016 12:59
Publisher:American Institute of Physics
ISSN:0021-9606
Additional Information:Copyright 2009 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 121, 5133 (2004) and may be found at http://scitation.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=JCPSA6000121000011005133000001&idtype=cvips&gifs=yes
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1063/1.1785780
Permanent URL: https://doi.org/10.5167/uzh-3180

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