Classical and quantum simulations of a lithium ion solvated by a mixed Stockmayer cluster

Electrolyte clusters as hydrogen sponges: diffusion Monte Carlo simulations

“…The black solid line is reproduced from ref. 26 and is the histogram of the radial distances of Li + from the center of mass for EC106. Adding one molecule of hydrogen produces the red (dashed) line in the same figure.…”

“…19,20 One needs only consider the extensive exploration of small to medium sized Lennard Jones clusters published to date, [21][22][23] to come to the realization that, by itself, the characterization of Electrolyte Clusters (ECs) remains in its infancy. [24][25][26][27][28] The cited works on Lennard Jones aggregates, [21][22][23] are only a small set of the vast literature, reflecting the complexity of the landscape described with just three parameter, if we include the number of aggregated particles as a degree of freedom. The systematic exploration of the parameter space of clusters of electrolytes, even with the simplest of mathematical models, is likely to require orders of magnitude more effort.…”

“…In recent investigations, the structure, classical thermodynamics, and ground state properties of ECs comprised of a lithium ion surrounded by points dipoles, are determined. [26][27][28] The largest of the systems investigated (EC106) is a mixture of two types of Stockmayer particles with parameters matching nitromethane (NM), for six and tetrahydrofuran (THF) for the remaining one hundred components. 26 The global minimum of EC106 features the charge on the surface surrounded by five NM dipoles segregated from the rest, wheareas Li + is between two solvation layers in the molten state.…”

“…[26][27][28] The largest of the systems investigated (EC106) is a mixture of two types of Stockmayer particles with parameters matching nitromethane (NM), for six and tetrahydrofuran (THF) for the remaining one hundred components. 26 The global minimum of EC106 features the charge on the surface surrounded by five NM dipoles segregated from the rest, wheareas Li + is between two solvation layers in the molten state. The solvated Li + has some unusual features.…”

“…The focus of this article is to determine the energy and structures of hydrogen molecules as they aggregate with two of the recently explored ECs, [26][27][28] the larger system EC106 mentioned earlier, and EC6, a Li + ion surrounded by six NM point dipoles. The smaller EC6-(H 2 ) x complexes are chosen for comparison, to verify the generality of the features we observe with hydrogen aggregated to EC106, and to obtain resolution on the sequential biding energy of hydrogen to ECs.…”