Abstract

This work systematically examines the interactions of alkali metal cations and their isoelectronic halide counterparts with up to six solvating Ar atoms (M+Arn and X–Arn, where M = Li, Na, K, and Rb; X = H, F, Cl, and Br; and n = 1–6) via full geometry optimizations with the MP2 method and robust, correlation-consistent quadruple-ζ (QZ) basis sets. 116 unique M+Arn and X–Arn stationary points have been characterized on the MP2/QZ potential energy surface. To the best of our knowledge, approximately two dozen of these stationary points have been reported here for the first time. Some of these new structures are either the lowest-energy stationary point for a particular cluster or energetically competitive with it. The CCSD(T) method was employed to perform additional single-point energy computations upon all MP2/QZ-optimized structures using the same basis set. CCSD(T)/QZ results indicate that internally solvated structures with the ion at/near the geometric center of the cluster have appreciably higher energies than those placing the ion on the periphery. While this study extends the prior investigations of M+Arn clusters found within the literature, it notably provides one of the first thorough characterizations of and comparisons to the corresponding negatively charged X–Arn clusters.

Department(s)

Chemistry

Comments

National Science Foundation, Grant CHE-166498

International Standard Serial Number (ISSN)

1520-5215; 1089-5639

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2024 American Chemical Society, All rights reserved.

Publication Date

16 Dec 2021

PubMed ID

34851634

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