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Theoretical scrutinization of nine benzoic acid dimers: Stability and energy decomposition analysis
Author(s) -
Petrović Ivana,
Milovanović Branislav,
Etinski Mihajlo,
Petković Milena
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25918
Subject(s) - dimer , chemistry , hydrogen bond , dissociation (chemistry) , stacking , bond dissociation energy , non covalent interactions , benzoic acid , monomer , density functional theory , interaction energy , computational chemistry , carboxylic acid , acceptor , chemical physics , molecular dynamics , molecule , polymer , organic chemistry , physics , condensed matter physics
Aromatic carboxylic acids are able to form diverse dimers and multimers due to their hydrogen bond donor and acceptor cites, as well as the aromatic rings. In this work, we examine nine benzoic acid dimers stabilized by hydrogen bonding and stacking interactions. Interacting quantum atoms methodology revealed that dominant attractive interactions in all of them, including hydrogen bonded systems, are due to exchange‐correlation. Coulomb interactions are significant only in the most stable dimer with a double hydrogen bond, although the corresponding energy term is almost two times lower compared to the nonclassical one. Since interacting quantum atoms approach treats monomers binding by considering electronic energy only, in order to examine dissociation kinetics we performed density functional theory‐based molecular dynamics simulations of selected stacked dimers: in 40% of the studied systems at 300 K thermal energy was sufficient to overpower barrier for dissociation within 1 ps, which resulted in the separation of the monomers, whereas 20% of them remained in the stacked position even after 5 ps. These results highlight the importance of noncovalent interactions, particularly weak stacking interactions, on the structure and dynamics of carboxylic acids and their derivatives.