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π⋅⋅⋅H + ⋅⋅⋅π Hydrogen Bonds and Their Lithium and Gold Analogues: MP2 and CASPT2 Calculations
Author(s) -
Grabowski Sławomir J.,
Ruipérez Fernando
Publication year - 2017
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.201700574
Subject(s) - natural bond orbital , chemistry , atoms in molecules , lithium (medication) , molecule , acetylene , computational chemistry , hydrogen bond , crystallography , chemical physics , density functional theory , organic chemistry , medicine , endocrinology
Molecular systems in which two simple π‐electron species, acetylene and ethylene, are linked by a cation located between them are analyzed in this study. In particular, the C 2 H 2 ⋅⋅⋅ M + ⋅⋅⋅ C 2 H 2 , C 2 H 4 ⋅⋅⋅ M + ⋅⋅⋅ C 2 H 2 , and C 2 H 4 ⋅⋅⋅ M + ⋅⋅⋅ C 2 H 4 complexes (M + =H + , Li + , Au + ) are calculated with the use of MP2 and CASPT2 methods. The Quantum Theory of Atoms in Molecules (QTAIM), energy decomposition analysis (EDA), and Natural Bond Orbital (NBO) approaches are applied to deepen the understanding of the nature of M + ⋅⋅⋅ π interactions in these complexes. It is found that the interactions in gold and proton complexes are characterized by at least partial covalency, whereas interactions in lithium complexes are rather electrostatic in nature.