Intermolecular interactions between PH2Cl and Ar–R（R = H,OH,NH2,CH3,Br,Cl,F,CN,NO2） were calculated by using MP2/aug-cc-p VDZ quantum chemical method.It has been shown from our calculations that the aromatic rings ...Intermolecular interactions between PH2Cl and Ar–R（R = H,OH,NH2,CH3,Br,Cl,F,CN,NO2） were calculated by using MP2/aug-cc-p VDZ quantum chemical method.It has been shown from our calculations that the aromatic rings with electron-withdrawing groups represent much weaker binding affinities than those with electron-donating groups.The charge-transfer interaction between PH2Cl and Ar–R plays an important role in the formation of pnicogen bond complexes,as revealed by NBO analysis.Nevertheless,AIM analysis shows that the nature of the interactions between PH2Cl and Ar–R is electrostatic,and the interaction energies of the complexes are correlated positively with the electron densities in the bond critical points（BCPs）.RDG/ELF graphical analyses were performed to visualize the positions and strengths of the pnicogen bonding,as well as the spatial change of the electron localization upon the formation of complexes.The π-type halogen bond was also calculated,and it has been revealed that the π-type pnicogen bond systems are more stable than the halogen bond ones.展开更多
The pnicogen bond interaction between different electron donors(anion, π-electron, heteroatom) and ECl3(E = As, P) was calculated by the method of MP2/aug-cc-p VTZ. It has been indicated that the pnicogen bonds of co...The pnicogen bond interaction between different electron donors(anion, π-electron, heteroatom) and ECl3(E = As, P) was calculated by the method of MP2/aug-cc-p VTZ. It has been indicated that the pnicogen bonds of complex formed by the anion and ECl3 are more stable than that by the neutral electron donor, in which the pnicogen bonds of complex formed by NH3 and ECl3 are the most stable, and that by H2S and ECl3 is the least stable. The nature of pnicogen bond interaction is the closed shell interaction by AIM analysis, and BCP electron density is positively correlated to the complex interaction energy. RDG and DDF graphical analyses are performed to visualize the nature of pnicogen bond interaction from different donors, the position and strength of the pnicogen bond interaction, as well as the rearrangement of electron density after the formation of pnicogen bond system.展开更多
基金Supported by the Science and Technology Project of Zhejiang Province(2016C33039)Natural Science Foundation of Zhejiang Province(LY14C030004)+2 种基金National Natural Science Foundation of China(21272211)Project of the Special Foundation for Provincial Research Institutes of Zhejiang Province,China(2017F50002)Science and Technology Planning Project of the Zhejiang Provincial Department of Water Resources(RB1608)
文摘Intermolecular interactions between PH2Cl and Ar–R（R = H,OH,NH2,CH3,Br,Cl,F,CN,NO2） were calculated by using MP2/aug-cc-p VDZ quantum chemical method.It has been shown from our calculations that the aromatic rings with electron-withdrawing groups represent much weaker binding affinities than those with electron-donating groups.The charge-transfer interaction between PH2Cl and Ar–R plays an important role in the formation of pnicogen bond complexes,as revealed by NBO analysis.Nevertheless,AIM analysis shows that the nature of the interactions between PH2Cl and Ar–R is electrostatic,and the interaction energies of the complexes are correlated positively with the electron densities in the bond critical points（BCPs）.RDG/ELF graphical analyses were performed to visualize the positions and strengths of the pnicogen bonding,as well as the spatial change of the electron localization upon the formation of complexes.The π-type halogen bond was also calculated,and it has been revealed that the π-type pnicogen bond systems are more stable than the halogen bond ones.
基金supported by the Public Technology Research Project(Analysis and Measurement)of Zhejiang Province(LGC19B070004)State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-environmental Sciences,Chinese Academy of Sciences(KF2018-15)Program for the Philosophy and Social Research in Zhejiang Province(19NDJC262YB)
文摘The pnicogen bond interaction between different electron donors(anion, π-electron, heteroatom) and ECl3(E = As, P) was calculated by the method of MP2/aug-cc-p VTZ. It has been indicated that the pnicogen bonds of complex formed by the anion and ECl3 are more stable than that by the neutral electron donor, in which the pnicogen bonds of complex formed by NH3 and ECl3 are the most stable, and that by H2S and ECl3 is the least stable. The nature of pnicogen bond interaction is the closed shell interaction by AIM analysis, and BCP electron density is positively correlated to the complex interaction energy. RDG and DDF graphical analyses are performed to visualize the nature of pnicogen bond interaction from different donors, the position and strength of the pnicogen bond interaction, as well as the rearrangement of electron density after the formation of pnicogen bond system.
