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

Chaudhari, Mangesh I.; Rempe, Susan B.; Pratt, Lawrence R.

doi:10.1063/1.4986244

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

Journal Article · Sat Oct 28 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4986244· OSTI ID:1474054

Chaudhari, Mangesh I. ^[1]; Rempe, Susan B. ^[1];

^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Engineering Sciences
Tulane Univ., New Orleans, LA (United States). Dept. of Chemical and Biomolecular Engineering

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.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1474054

Alternate ID(s):: OSTI ID: 1389688

Report Number(s):: SAND-2018-10151J; 667915

Journal Information:: Journal of Chemical Physics, Vol. 147, Issue 16; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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