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Title: Interaction Potential of Al3+ In Water From First Principles Calculations

Abstract

We present a parametrization of the interaction potential for Al3+ in water from first principles calculations. We have performed a critical study of the Al3+–water interaction using sequences of correlation consistent basis sets that approach the complete basis set limit and include core-valence correlation effects. We suggest as minimum theoretical requirements treatment of the electron correlation at the MP2 level of theory using a triple zeta quality basis set that accounts for the effect of core-valence correlation. The latter amounts for an increase of ~5 kcal/mol (3%) to the stabilization energy, a shortening of 0.015 Å in the Al–O distance, and an increase of 22?cm-1 in the harmonic frequency of the Al–O vibration. This is the first time that core-valence effects were investigated for this system. The stabilization energy of the Al3+(H2O) cluster is 201 kcal/mol and the corresponding Al–O bond length is 1.719 Å at the MP2 level of theory with the cc-pwCVQZ basis set. This minimum is metastable with respect to the Al2++H2O+ asymptote since even the second ionization potential (IP) of Al is larger than the first IP of water. The hexa-aqua cluster Al3+(H2O)6 is, however, stable upon dissociation to Al3+(H2O)5+H2O by 64.8 kcal/mol, demonstrating the capacitymore » of “effective” solvation in stabilizing the charge on the cation. The optimal structures of the n=5 and 6 clusters (having C2v and Th symmetries, respectively) and their harmonic vibrational frequencies are the first ones reported at the MP2 level with basis sets of this size. Core-valence correlation effects for the n=6 cluster are found to be of similar magnitude with those observed for the n=1 cluster. The stabilization energy of the n=6 cluster with respect to its fragments is 723.7 kcal/mol and the corresponding Al–O distance is 1.911 Å. These results were used in order to parametrize a pairwise-additive interaction potential for aluminum–water interaction that was grafted onto the Toukan–Rahman interaction potential for water. The potential model reproduces the ab initio results for Al3+(H2O)6 within 2.0 kcal/mol for the stabilization energy and 0.003 Å for R(Al–O) distance. Using this potential we estimated the enthalpy of solvation of Al3+ to be -1106±6 kcal/mol, therefore favoring the lower value of the experimentally obtained data (-1115 and -1140 kcal/mol, respectively). In addition, we calculate the first peak of the Al–O radial distribution function at 1.885 Å, in excellent agreement with x-ray diffraction studies that suggest a peak at 1.882±0.004 Å. We compute the first peak of the Al–H radial distribution function at 2.473 Å and the average angle between the plane of a water molecule and the Al–O vector at -28.27°.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [2]
  1. EMSL, Pacific Northwest National Lab
  2. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1543427
Report Number(s):
PNNL-SA-28613
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 106; Journal Issue: 23
Country of Publication:
United States
Language:
English

Citation Formats

Wasserman, Evgeny, Wasserman, Evgeny, Rustad, James R., and Xantheas, Sotiris S. Interaction Potential of Al3+ In Water From First Principles Calculations. United States: N. p., 1997. Web. doi:10.1063/1.473866.
Wasserman, Evgeny, Wasserman, Evgeny, Rustad, James R., & Xantheas, Sotiris S. Interaction Potential of Al3+ In Water From First Principles Calculations. United States. doi:10.1063/1.473866.
Wasserman, Evgeny, Wasserman, Evgeny, Rustad, James R., and Xantheas, Sotiris S. Sun . "Interaction Potential of Al3+ In Water From First Principles Calculations". United States. doi:10.1063/1.473866.
@article{osti_1543427,
title = {Interaction Potential of Al3+ In Water From First Principles Calculations},
author = {Wasserman, Evgeny and Wasserman, Evgeny and Rustad, James R. and Xantheas, Sotiris S.},
abstractNote = {We present a parametrization of the interaction potential for Al3+ in water from first principles calculations. We have performed a critical study of the Al3+–water interaction using sequences of correlation consistent basis sets that approach the complete basis set limit and include core-valence correlation effects. We suggest as minimum theoretical requirements treatment of the electron correlation at the MP2 level of theory using a triple zeta quality basis set that accounts for the effect of core-valence correlation. The latter amounts for an increase of ~5 kcal/mol (3%) to the stabilization energy, a shortening of 0.015 Å in the Al–O distance, and an increase of 22?cm-1 in the harmonic frequency of the Al–O vibration. This is the first time that core-valence effects were investigated for this system. The stabilization energy of the Al3+(H2O) cluster is 201 kcal/mol and the corresponding Al–O bond length is 1.719 Å at the MP2 level of theory with the cc-pwCVQZ basis set. This minimum is metastable with respect to the Al2++H2O+ asymptote since even the second ionization potential (IP) of Al is larger than the first IP of water. The hexa-aqua cluster Al3+(H2O)6 is, however, stable upon dissociation to Al3+(H2O)5+H2O by 64.8 kcal/mol, demonstrating the capacity of “effective” solvation in stabilizing the charge on the cation. The optimal structures of the n=5 and 6 clusters (having C2v and Th symmetries, respectively) and their harmonic vibrational frequencies are the first ones reported at the MP2 level with basis sets of this size. Core-valence correlation effects for the n=6 cluster are found to be of similar magnitude with those observed for the n=1 cluster. The stabilization energy of the n=6 cluster with respect to its fragments is 723.7 kcal/mol and the corresponding Al–O distance is 1.911 Å. These results were used in order to parametrize a pairwise-additive interaction potential for aluminum–water interaction that was grafted onto the Toukan–Rahman interaction potential for water. The potential model reproduces the ab initio results for Al3+(H2O)6 within 2.0 kcal/mol for the stabilization energy and 0.003 Å for R(Al–O) distance. Using this potential we estimated the enthalpy of solvation of Al3+ to be -1106±6 kcal/mol, therefore favoring the lower value of the experimentally obtained data (-1115 and -1140 kcal/mol, respectively). In addition, we calculate the first peak of the Al–O radial distribution function at 1.885 Å, in excellent agreement with x-ray diffraction studies that suggest a peak at 1.882±0.004 Å. We compute the first peak of the Al–H radial distribution function at 2.473 Å and the average angle between the plane of a water molecule and the Al–O vector at -28.27°.},
doi = {10.1063/1.473866},
journal = {Journal of Chemical Physics},
number = 23,
volume = 106,
place = {United States},
year = {1997},
month = {6}
}

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