A thermodynamic view on the microsolvation of ions by rare gas: application to Li<sup>+</sup> with argon

Guimarães, Marcilio N.; Almeida, Marcos de; Marques, Jorge M. C.; Prudente, Frederico V.

doi:10.1039/d0cp01283a

Cited by 9 publications

(10 citation statements)

References 49 publications

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“…In turn, this behavior in the c V curve was observed in a previous work [24], where the Li + Ar n clusters with n = 33, 34 and 38 also presented a peak around 50 K. In that paper [24], the peak was associated to the melting of the external solvation shell, which is likely to be similar for the clusters studied here. Furthermore, the amplitude of such peak for smaller cluster sizes in Figure 4 is similar to that previously reported [24] for Li + Ar 38 , whose global minimum structure has a completed third solvation shell with 24 argon atoms (see Table S2 and Figure S2). Indeed, the total number of argon atoms in the external solvation shells for n = 41, 42, 44, 50, 52, and 53 did not differ too much from that value (cf.…”

Section: Ptmc Calculationssupporting

confidence: 86%

“…We employ our own implementation of the parallel tempering Monte Carlo (PTMC) method to calculate the heat capacity as a function of temperature for some specific cluster sizes. Since the method has been previously described [24,39], here, we just offer an overview of the main features and present some modifications introduced for this study.…”

Section: Parallel Tempering Monte Carlo Methodsmentioning

confidence: 99%

“…In Equation (4), distance vector R is referred to the vector of the center of mass coordinates of the cluster (R CM ) and R cut is a parameter that establishes the volume of the available configurational space. As in our previous work [24], we define R cut = αD max , where α = 1.4 and D max is the distance of the farthest atom from the center of mass of the initial structure. Since five low-energy minima are considered as possible departing structures for each simulation, one has five values for D max .…”

Section: Parallel Tempering Monte Carlo Methodsmentioning

confidence: 99%

“…Additionally, the closure of the first solvation shell in these systems is characterized by strong magic numbers [21,23], which may be attenuated by including three-body terms in the potential energy surface [23]. Another fingerprint for identifying structural features of the microsolvation clusters is heat capacity, which indicates [24] distinct temperatures for melting the first and the second solvation shells of Li + Ar n . In fact, it has been shown that Li + Ar n clusters show a rigid first solvation shell in comparison with the fluxional character of the second solvation shell [25].…”

Section: Introductionmentioning

confidence: 99%

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Structure and Thermodynamics of Li+Arn Clusters beyond the Second Solvation Shell

Marques,

Prudente

2024

Symmetry

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Small Li+Arn clusters are employed in this work as model systems to study microsolvation. Although first and second solvation shells are expected to be the most relevant ones for this type of atomic solvents, it is also interesting to explore larger clusters in order to identify the influence of external atoms on structural and thermodynamic properties. In this work, we perform a global geometry optimization for Li+Arn clusters (with n=41−100) and parallel tempering Monte Carlo (PTMC) simulations for some selected sizes. The results show that global minimum structures of large clusters always have 6 argon atoms in the first solvation shell while maintaining the number of 14 or 16 argon atoms in the second one. By contrast, third and fourth solvation shells vary significantly the number of argon atoms with the cluster size, and other shells can hardly be assigned due to the reduced influence of Li+ on the external argon atoms for large clusters. In turn, PTMC calculations show that the melting of the most external solvation shells of large microsolvation clusters occurs at T∼50K, which is independent of cluster size. Structural transitions can be observed between quasi-degenerated structures at low temperatures. Moreover, the present results highlight the fluxional character of the external solvation shells of these large Li+Arn clusters, which may be seen as typical “snowball” structures.

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Section: Ptmc Calculationssupporting

confidence: 86%

Section: Parallel Tempering Monte Carlo Methodsmentioning

confidence: 99%

Section: Parallel Tempering Monte Carlo Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure and Thermodynamics of Li+Arn Clusters beyond the Second Solvation Shell

Marques,

Prudente

2024

Symmetry

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“…For example, a broad range of experimental and theoretical studies have examined singly charged alkali metal cations in this context (M + Ng n , where M = Li, Na, K, etc. ). − In contrast, fewer investigations of their isoelectronic halide anion counterparts (X – Ng n , where X = H, F, Cl, etc. ) have been reported, particularly for n ≥ 3. − …”

Section: Introductionmentioning

confidence: 99%

Solvation of Isoelectronic Halide and Alkali Metal Ions by Argon Atoms

2021

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This work systematically examines the interactions of alkali metal cations and their isoelectronic halide counterparts with up to six solvating Ar atoms (M + Ar n and X − Ar n , 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 + Ar n and X − Ar n 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 + Ar n clusters found within the literature, it notably provides one of the first thorough characterizations of and comparisons to the corresponding negatively charged X − Ar n clusters.

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Energetics and spectroscopic studies of CNO(‐)(H2O)n clusters and the temperature dependencies of the isomers: An approach based on a combined recipe of parallel tempering and quantum chemical methods

Naskar,

Talukder

2024

J Comput Chem

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A system associated with several number of weak interactions supports numerous number of stable structures within a narrow range of energy. Often, a deterministic search method fails to locate the global minimum geometry as well as important local minimum isomers for such systems. Therefore, in this work, the stochastic search technique, namely parallel tempering, has been executed on the quantum chemical surface of the system for –8 to generate global minimum as well as several number of local minimum isomers. IR spectrum can act as the fingerprint property for such system to be identified. Thus, IR spectroscopic features have also been included in this work. Vertical detachment energy has also been calculated to obtain clear information about number of water molecules in several spheres around the central anion. In addition, in a real experimental scenario, not only the global but also the local minimum isomers play an important role in determining the average value of a particular physically observable property. Therefore, the relative conformational populations have been determined for all the evaluated structures for the temperature range between 20K and 400K. Further to understand the phase change behavior, the configurational heat capacities have also been calculated for different sizes.

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A thermodynamic view on the microsolvation of ions by rare gas: application to Li⁺ with argon

Abstract: Parallel tempering Monte Carlo calculations on the Li+Arn microsolvation clusters have shown that the two peaks appearing in the heat capacity curve as a function of temperature correspond to the melting of the second and first solvation shells.

Cited by 9 publications

References 49 publications

Structure and Thermodynamics of Li+Arn Clusters beyond the Second Solvation Shell

Structure and Thermodynamics of Li+Arn Clusters beyond the Second Solvation Shell

Solvation of Isoelectronic Halide and Alkali Metal Ions by Argon Atoms

Energetics and spectroscopic studies of CNO(‐)(H2O)n clusters and the temperature dependencies of the isomers: An approach based on a combined recipe of parallel tempering and quantum chemical methods

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A thermodynamic view on the microsolvation of ions by rare gas: application to Li+ with argon

Abstract: Parallel tempering Monte Carlo calculations on the Li+Arn microsolvation clusters have shown that the two peaks appearing in the heat capacity curve as a function of temperature correspond to the melting of the second and first solvation shells.

Cited by 9 publications

References 49 publications

Structure and Thermodynamics of Li+Arn Clusters beyond the Second Solvation Shell

Structure and Thermodynamics of Li+Arn Clusters beyond the Second Solvation Shell

Solvation of Isoelectronic Halide and Alkali Metal Ions by Argon Atoms

Energetics and spectroscopic studies of CNO(‐)(H2O)n clusters and the temperature dependencies of the isomers: An approach based on a combined recipe of parallel tempering and quantum chemical methods

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A thermodynamic view on the microsolvation of ions by rare gas: application to Li⁺ with argon