caa a22 4500 605511594 CHVBK 20210128100651.0 cr unu---uuuuu 210128e20150701xx s 000 0 eng 10.1007/s00894-015-2727-9 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2727-9 An ab initio study on tunability of σ -hole interactions in XHS:PH2Y and XH2P:SHY complexes (X = F, Cl, Br; Y = H, OH, OCH3, CH3, C2H5, and NH2) [Elektronische Daten] [Mehdi Esrafili, Nafiseh Mohammadirad] Quantum chemical calculations are performed to investigate the tunability of σ-hole interactions in chalcogen-bonded XHS:PH2Y and pnicogen-bonded XH2P:SHY complexes, where X = F, Cl, Br and Y = H, OH, OCH3, CH3, C2H5, NH2. The formation of these binary complexes can be understood in terms of molecular electrostatic potentials (MEPs), considering the P and S atoms as an electron acceptor or an electron donor in the chalcogen and pnicogen bonds. The strength of the XHS:PH2Y and XH2P:SHY complexes for a given Y increases as follows: X = Br < Cl < F. In addition, an acceptable linear relationship is found between the interaction energies and the magnitudes of the product of most positive and negative MEPs. This finding along with the electron density difference maps provides a clear picture of the electrostatic nature of the interactions in the XHS:PH2Y and XH2P:SHY complexes. The calculated spin-spin coupling constants across the chalcogen bond interactions in the XHS:PH2Y complexes display a quadratic dependence with the P···S binding distance. Springer-Verlag Berlin Heidelberg, 2015 Chalcogen bond nationallicence DFT nationallicence MEP nationallicence Pnicogen bond nationallicence σ -hole nationallicence Esrafili Mehdi Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, P.O. Box: 5513864596, Maragheh, Iran aut Mohammadirad Nafiseh Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, P.O. Box: 5513864596, Maragheh, Iran aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/7(2015-07-01), 1-8 1610-2940 21:7<1 2015 21 894 https://doi.org/10.1007/s00894-015-2727-9 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2727-9 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Esrafili Mehdi Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, P.O. Box: 5513864596, Maragheh, Iran aut NATIONALLICENCE 700 1- Mohammadirad Nafiseh Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, P.O. Box: 5513864596, Maragheh, Iran aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/7(2015-07-01), 1-8 1610-2940 21:7<1 2015 21 894