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Title: An extended basis set ab initio study of Li +(H 2O) n, n=1-6

Abstract

We report that the structures, binding energies, and enthalpies of small molecular clusters incorporating a single lithium cation and up through six waters have been determined with extended Gaussian basis sets using Hartree–Fock and post-Hartree–Fock methods. The resulting properties are analyzed with respect to both basis set completeness and degree of correlation recovery, including core–core and core–valence effects. Although the lithium–water interaction is largely electrostatic in nature, small basis sets, lacking in polarization and near-valence diffuse functions, drastically overestimate the strength of the bond (by 20 kcal/mol or more) and underestimate the Li +...O distance by up to 0.1 Å. Their poor performance is attributable to inherent errors in describing the electric moments and polarizability of water and to large basis set superposition errors. Thus, the accuracy with which the fundamental lithium–water interaction could be modeled was primarily dependent on the quality of the Gaussian basis set and not upon the level of correlation recovery. Basis set enlargement and correlation effects both tend to reduce the strength of the Li +(H 2O) bond, but produce corrections of opposite sign for the Li +...O bond length. Finally, although correlation effects play a minor role in describing the lithium–water interaction, as themore » size of the cluster increases and the number of waters involved in multiple hydrogen bonds grows, correlation recovery can become significant.« less

Authors:
 [1];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1491727
Report Number(s):
PNL-SA-23188
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 100; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Feller, David, Glendening, Eric D., Kendall, Rick A., and Peterson, Kirk A. An extended basis set ab initio study of Li+(H2O)n,n=1-6. United States: N. p., 1994. Web. doi:10.1063/1.467217.
Feller, David, Glendening, Eric D., Kendall, Rick A., & Peterson, Kirk A. An extended basis set ab initio study of Li+(H2O)n,n=1-6. United States. doi:10.1063/1.467217.
Feller, David, Glendening, Eric D., Kendall, Rick A., and Peterson, Kirk A. Fri . "An extended basis set ab initio study of Li+(H2O)n,n=1-6". United States. doi:10.1063/1.467217. https://www.osti.gov/servlets/purl/1491727.
@article{osti_1491727,
title = {An extended basis set ab initio study of Li+(H2O)n,n=1-6},
author = {Feller, David and Glendening, Eric D. and Kendall, Rick A. and Peterson, Kirk A.},
abstractNote = {We report that the structures, binding energies, and enthalpies of small molecular clusters incorporating a single lithium cation and up through six waters have been determined with extended Gaussian basis sets using Hartree–Fock and post-Hartree–Fock methods. The resulting properties are analyzed with respect to both basis set completeness and degree of correlation recovery, including core–core and core–valence effects. Although the lithium–water interaction is largely electrostatic in nature, small basis sets, lacking in polarization and near-valence diffuse functions, drastically overestimate the strength of the bond (by 20 kcal/mol or more) and underestimate the Li+...O distance by up to 0.1 Å. Their poor performance is attributable to inherent errors in describing the electric moments and polarizability of water and to large basis set superposition errors. Thus, the accuracy with which the fundamental lithium–water interaction could be modeled was primarily dependent on the quality of the Gaussian basis set and not upon the level of correlation recovery. Basis set enlargement and correlation effects both tend to reduce the strength of the Li+(H2O) bond, but produce corrections of opposite sign for the Li+...O bond length. Finally, although correlation effects play a minor role in describing the lithium–water interaction, as the size of the cluster increases and the number of waters involved in multiple hydrogen bonds grows, correlation recovery can become significant.},
doi = {10.1063/1.467217},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 7,
volume = 100,
place = {United States},
year = {1994},
month = {4}
}

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Works referenced in this record:

The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
journal, October 1970