title: Application of polarizable ellipsoidal force field model to pnicogen bonds.
abstract: Noncovalent interactions, such as hydrogen bonds and halogen bonds, are frequently used in drug designing and crystal engineering. Recently, a novel noncovalent pnicogen bonds have been identified as an important driving force in crystal structures with similar bonding mechanisms as hydrogen bond and halogen bond. Although the pnicogen bond is highly anisotropic, the pnicogen bond angles range from 160° to 180° due to the complicated substituent effects. To understand the anisotropic characters of pnicogen bond, a modification of the polarizable ellipsoidal force field (PEff) model previously used to define halogen bonds was proposed in this work. The potential energy surfaces (PESs) of mono- and polysubstituted PH3 -NH3 complexes were calculated at CCSD(T), MP2, and density functional theory levels and were used to examine the modified PEff model. The results indicate that the modified PEff model can precisely characterize pnicogen bond. The root mean squared error of PES obtained with PEff model is less than 0.5 kcal/mol, compared with MP2 results. In addition, the modified PEff model may be applied to other noncovalent bond interactions, which is important to understand the role of intermolecular interactions in the self-assembly structures.
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, School of Chemistry & Chemical Engineering, Shandong University, Jinan, 250100, People's Republic of China.
authors.forename: Fang
authors.initials: F
authors.lastname: Liu
authors.forename: Likai
authors.initials: L
authors.lastname: Du
authors.forename: Jun
authors.initials: J
authors.lastname: Gao
authors.forename: Lili
authors.initials: L
authors.lastname: Wang
authors.forename: Bo
authors.initials: B
authors.lastname: Song
authors.forename: Chengbu
authors.initials: C
authors.lastname: Liu
mesh_terms: D000965:Antimony / Q000737:chemistry*; D001151:Arsenic / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010758:Phosphorus / Q000737:chemistry*; D011789:Quantum Theory; D055672:Static Electricity; D013816:Thermodynamics
chemical_list: D010758:Phosphorus; D000965:Antimony; D001151:Arsenic
keywords: anisotropic; electrostatic potential; noncovalent interaction; pnicogen bond; polarizable force field