skip to main content

DOE PAGESDOE PAGES

Title: Quasi-chemical theory of F - (aq): The “no split occupancies rule” revisited

We use ab initio molecular dynamics (AIMD) calculations and quasi-chemical theory (QCT) to study the inner-shell structure of F-(aq) and to evaluate that single-ion free energy under standard conditions. Following the “no split occupancies” rule, QCT calculations yield a free energy value of -101 kcal/mol under these conditions, in encouraging agreement with tabulated values (-111 kcal/mol). The AIMD calculations served only to guide the definition of an effective inner-shell constraint. QCT naturally includes quantum mechanical effects that can be concerning in more primitive calculations, including electronic polarizability and induction, electron density transfer, electron correlation, molecular/atomic cooperative interactions generally, molecular flexibility, and zero-point motion. No direct assessment of the contribution of dispersion contributions to the internal energies has been attempted here, however. We anticipate that other aqueous halide ions might be treated successfully with QCT, provided that the structure of the underlying statistical mechanical theory is absorbed, i.e., that the “no split occupancies” rule is recognized.
Authors:
 [1] ;  [1] ; ORCiD logo [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Engineering Sciences
  2. Tulane Univ., New Orleans, LA (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Report Number(s):
SAND-2018-10151J
Journal ID: ISSN 0021-9606; 667915
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1474054
Alternate Identifier(s):
OSTI ID: 1389688

Chaudhari, Mangesh I., Rempe, Susan B., and Pratt, Lawrence R.. Quasi-chemical theory of F - (aq): The “no split occupancies rule” revisited. United States: N. p., Web. doi:10.1063/1.4986244.
Chaudhari, Mangesh I., Rempe, Susan B., & Pratt, Lawrence R.. Quasi-chemical theory of F - (aq): The “no split occupancies rule” revisited. United States. doi:10.1063/1.4986244.
Chaudhari, Mangesh I., Rempe, Susan B., and Pratt, Lawrence R.. 2017. "Quasi-chemical theory of F - (aq): The “no split occupancies rule” revisited". United States. doi:10.1063/1.4986244. https://www.osti.gov/servlets/purl/1474054.
@article{osti_1474054,
title = {Quasi-chemical theory of F - (aq): The “no split occupancies rule” revisited},
author = {Chaudhari, Mangesh I. and Rempe, Susan B. and Pratt, Lawrence R.},
abstractNote = {We use ab initio molecular dynamics (AIMD) calculations and quasi-chemical theory (QCT) to study the inner-shell structure of F-(aq) and to evaluate that single-ion free energy under standard conditions. Following the “no split occupancies” rule, QCT calculations yield a free energy value of -101 kcal/mol under these conditions, in encouraging agreement with tabulated values (-111 kcal/mol). The AIMD calculations served only to guide the definition of an effective inner-shell constraint. QCT naturally includes quantum mechanical effects that can be concerning in more primitive calculations, including electronic polarizability and induction, electron density transfer, electron correlation, molecular/atomic cooperative interactions generally, molecular flexibility, and zero-point motion. No direct assessment of the contribution of dispersion contributions to the internal energies has been attempted here, however. We anticipate that other aqueous halide ions might be treated successfully with QCT, provided that the structure of the underlying statistical mechanical theory is absorbed, i.e., that the “no split occupancies” rule is recognized.},
doi = {10.1063/1.4986244},
journal = {Journal of Chemical Physics},
number = 16,
volume = 147,
place = {United States},
year = {2017},
month = {10}
}