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Title: Multipole moments of water molecules and the aqueous solvation of monovalent ions

Authors:
; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1398712
Grant/Contract Number:
NA-0002006
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Molecular Liquids
Additional Journal Information:
Journal Volume: 228; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-08 22:27:58; Journal ID: ISSN 0167-7322
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English

Citation Formats

Rodgers, Jocelyn M., and Ichiye, Toshiko. Multipole moments of water molecules and the aqueous solvation of monovalent ions. Netherlands: N. p., 2017. Web. doi:10.1016/j.molliq.2016.10.007.
Rodgers, Jocelyn M., & Ichiye, Toshiko. Multipole moments of water molecules and the aqueous solvation of monovalent ions. Netherlands. doi:10.1016/j.molliq.2016.10.007.
Rodgers, Jocelyn M., and Ichiye, Toshiko. Wed . "Multipole moments of water molecules and the aqueous solvation of monovalent ions". Netherlands. doi:10.1016/j.molliq.2016.10.007.
@article{osti_1398712,
title = {Multipole moments of water molecules and the aqueous solvation of monovalent ions},
author = {Rodgers, Jocelyn M. and Ichiye, Toshiko},
abstractNote = {},
doi = {10.1016/j.molliq.2016.10.007},
journal = {Journal of Molecular Liquids},
number = C,
volume = 228,
place = {Netherlands},
year = {Wed Feb 01 00:00:00 EST 2017},
month = {Wed Feb 01 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.molliq.2016.10.007

Citation Metrics:
Cited by: 3works
Citation information provided by
Web of Science

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  • We have used an induction model including dipole, dipole{endash}quadrupole, quadrupole{endash}quadrupole polarizability and first hyperpolarizability as well as fixed octopole and hexadecapole moments to study the electric field in ice. The self-consistent induction calculations gave an average total dipole moment of 3.09 D, a 67{percent} increase over the dipole moment of an isolated water molecule. A previous, more approximate induction model study by Coulson and Eisenberg [Proc. R. Soc. Lond. A {bold 291}, 445 (1966)] suggested a significantly smaller average value of 2.6 D. This value has been used extensively in recent years as a reference point in the development ofmore » various polarizable interaction potentials for water as well as for assessment of the convergence of water cluster properties to those of bulk. The reason for this difference is not due to approximations made in the computational scheme of Coulson and Eisenberg but rather due to the use of less accurate values for the molecular multipoles in these earlier calculations. {copyright} {ital 1998 American Institute of Physics.}« less
  • We have calculated {ital molecular} multipole moments for water molecules in clusters and in ice Ih by partitioning the charge density obtained from first principles calculations. Various schemes for dividing the electronic charge density among the water molecules were used. They include Bader{close_quote}s zero flux surfaces and Voronoi partitioning schemes. A comparison was also made with an induction model including dipole, dipole-quadrupole, quadrupole-quadrupole polarizability and first hyperpolarizability as well as fixed octopole and hexadecapole moments. We have found that the different density partitioning schemes lead to widely different values for the molecular multipoles, illustrating how poorly defined molecular multipoles aremore » in clusters and condensed environments. For instance, the magnitude of the molecular dipole moment in ice Ih ranges between 2.3 D and 3.1 D depending on the partitioning scheme used. Within each scheme, though, the value for the molecular dipole moment in ice is larger than in the hexamer. The magnitude of the molecular dipole moment in the clusters shows a monotonic increase from the gas phase value to the one in ice Ih, with the molecular dipole moment in the water ring hexamer being smaller than the one in ice Ih for all the partitioning schemes used. {copyright} {ital 1999 American Institute of Physics.}« less
  • The relation between enthalpies of solvation of onium ions, BH/sup +/, by one water molecule, -..delta..H/sup 0//sub 0/ /sub 1/, and by four water molecules, -..delta..H/sup 0//sub 0/ /sub 4/, is constant for most onium ions: ..delta..H/sup 0//sub 0/ /sub 4//..delta..H/sup 0//sub 0/ /sub 1/ is 2.8 +/- 0.1 for all oxonium ions and monoprotonic ammonium and pyridium ions, and 3.1 +/- 0.1 for polyprotonic ammonium ions. These relations, in conjunction with the correlation between ..delta..H/sup 0//sub 0/ /sub 1/ and the proton affinity difference (..delta..PA = PA(B) - PA(H/sub 2/O)), allow the prediction of the total four-molecule specific hydrationmore » energy -..delta..H/sup 0//sub 0/ /sub 4/ for all onium ions within the experimental accuracy of +/-3 kcal mol/sup -1/. The observed (or predicted) fourfold specific relative hydration energies simulate closely the relative bulk hydration enthalpies for most ions. In other words, for most onium ions differential hydration effects are determined by specific hydrogen-bonding interactions. Deviations are useful to identify bulk solvation effects. For example, such deviations indicate attenuated bulk solvation of ions with phenyl substituents. 5 figures, 2 tables.« less