Ion-Stockmayer clusters: Minima, classical thermodynamics, and variational ground state estimates of Li+(CH3NO2)<i>n</i> (<i>n</i> = 1–20)

Curotto, E.

doi:10.1063/1.4936587

Cited by 8 publications

(15 citation statements)

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“…For the present model, the vertices of the octahedral first layer are coordinated asymmetrically, leaving the octahedral layer on the surface of the ( D T ) 12 cluster. The latter is not sufficiently large to observe the braid to ring structure we find in our work with Li + ( D N ) n clusters . When the charge is removed, as in ( D N ) 6 ( D T ) 12 , and Li( D N ) 6 ( D T ) 12 , the ( D N ) 6 cluster forms a hexagonal ring embedded in an icosahedral‐like network of the ( D T ) 12 cluster.…”

Section: Methods and Resultsmentioning

confidence: 62%

“…We employ a parallel implementation of the genetic algorithm to search for the most important geometries of each of the three clusters. A total of 12 generations are sufficient to reach convergence . We use 23 processors, each tasked to create 100 children using the cross‐over operator for each generation.…”

Section: Methods and Resultsmentioning

confidence: 99%

“…It corresponds to the n = 18 system, a solvated ion with the first sheath having octahedral symmetry, weakly bound to an eight‐membered and a four‐membered ring crowning a vertex of the octahedron. The nuclear quantum effects on the ground state are substantial . In the present article we propose the investigation of three related systems: Li + ( D N ) 6 ( D T ) 12 , Li( D N ) 6 ( D T ) 12 , and ( D N ) 6 ( D T ) 12 , to begin answering some of the questions the previous studies have generated.…”

Section: Introductionmentioning

confidence: 96%

“…Arguably the simplest model of the fundamental interactions of an ion‐polar solvent mixture is the ion‐Stockmayer model . Even though the body of knowledge gathered to date on clusters is vast, we find surprisingly little work dedicated to the study of Stockmayer and ion‐Stockmayer clusters in the literature. The present goals are of fundamental importance for the research and development of lithium ion batteries, as a practical application.…”

Section: Introductionmentioning

confidence: 99%

“…In a recent study, we carry out structural optimization, classical NVT ensemble, and variational Monte Carlo simulations of ion Stockmayer clusters Li + ( D N ) n ( n = 1 − 20) where D N represents a dipolar particle parameterized to approximate the nitromethane molecule. We do this to choose reasonable values of the ion‐Stockmayer parameters rather than varying systematically the parameter space .…”

Section: Introductionmentioning

confidence: 99%

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Re‐weighted random series path integral simulations of molecular clusters: Applications to lithium solvated by a mixed Stockmayer cluster

Hyers

Fodor

Bierwisch

et al. 2019

Int J of Quantum Chemistry

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Nuclear quantum effects in finite temperature simulations of molecular clusters are determined by taking advantage of a recently developed method based on the Feynman Path Integral. The structural and thermodynamic properties, including the nuclear quantum effects are determined for three Stockmayer clusters. The ionic system contain a lithium ion solvated by six strong dipoles and 12 weaker ones. The presence of the ion in the mixed Stockmayer cluster drastically enhances the fluxional nature of the less polar components which occupy the second solvation layer, whereas the neutral counterpart has the effect of reducing it. The nuclear quantum effects are significant at room temperature and above for the solvated ionic system. These are attributable to two factors: (a) the lightness of the lithium ion and (b) the stiffness of the ion-dipole interactions. At 300 K, the difference between the fully converged quantum and the classical heat capacities is about 1.3 K B for the ionic cluster. This difference is about 10 SDs obtained from 95% confidence estimates of the statistical fluctuations. Cubic convergence is confirmed for temperatures as low as 50 K by regression analysis. The nuclear quantum effects do not change the peak melting temperature of the cluster. K E Y W O R D S nuclear quantum effects, lithium ion, re-weighted random series path integral, generalized coordinates, stereographic projections 1 | INTRODUCTIONClusters are gas phase nano-sized aggregates of matter, they are vitally important for technological advances, and can serve as model systems to untangle and simplify the investigation of otherwise intractable problems at the fundamental level using a combination of theoretical and experimental methods. The contributions along these two lines are so numerous that it would be impossible to provide a meaningful comprehensive review of the literature [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] within the confines of a research article. One fundamental issue that can be addressed theoretically and experimentally using clusters is the determination of the nuclear quantum effects on the dynamics [20] and thermodynamics of microsolvation. Learning about the timescales of solvent rearrangement dynamics as a solute particle suddenly changes its charged state, and how these are impacted by the interaction parameters, the nuclear quantum effects, and the size of the cluster, are the long term objectives of our efforts. In this work we focus on the equilibrium properties since these will provide the needed insight as well as the starting points for later quantum dynamic studies.The determination of nuclear quantum effects in finite temperature simulations of molecular clusters, such as those concerning us here, remains challenging. In these complex systems, the intramolecular degrees of freedom are associated with frequencies that are many times larger than

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