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Importance of Structural Motifs in Liquid Hydrogen Fluoride
Author(s) -
Perlt Eva,
Friedrich Joachim,
von Domaros Michael,
Kirchner Barbara
Publication year - 2011
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100592
Subject(s) - pentamer , basis set , coupled cluster , perturbation theory (quantum mechanics) , chemistry , quantum chemistry , hydrogen fluoride , cluster (spacecraft) , density functional theory , electronic structure , electronic correlation , quantum , molecular physics , computational chemistry , molecule , chemical physics , statistical physics , quantum mechanics , physics , supramolecular chemistry , inorganic chemistry , biochemistry , organic chemistry , computer science , programming language
The investigation of liquid phases by means of accurate electronic structure methods is a demanding task due to the high computational effort. We applied second‐order Møller–Plesset perturbation theory and high‐level quantum chemical calculations using the coupled‐cluster method with single, double and perturbative triple excitations in combination with Dunnings correlation‐consistent basis sets up to quintuple ζ quality. Based on these calculations, we extrapolated the correlation energy to the basis set limit in order to improve the results even further. For comparison to the correlated electronic structure methods, density functional calculations employing different functionals are presented as well. The investigated species are a cyclic pentamer as well as a set of branched structures. The quantum cluster equilibrium method is employed for the investigation of the liquid‐phase structure of hydrogen fluoride. The pentamer is found to be present to a high extent and in the case of the MP2/QZVP data, its presence improves the results significantly. Accounting for branched structures slightly improves results, so that they are found to be present but not to dominate in liquid hydrogen fluoride. Concerning both the interaction energy and the result of the quantum cluster equilibrium calculation the basis set has a major influence, whereas the difference between Møller–Plesset perturbation theory and coupled‐cluster calculations is less pronounced.