B3LYP/6-311＋＋G level were employed to obtain the optimized geometries and calculated frequency of HCOCl and HOCl complexes.Five stable isomers were obtained,and the one with ClO-H…O=C hydrogen bond was the most sta...B3LYP/6-311＋＋G level were employed to obtain the optimized geometries and calculated frequency of HCOCl and HOCl complexes.Five stable isomers were obtained,and the one with ClO-H…O=C hydrogen bond was the most stable among five stable isomers,the BSSE and ZPE corrected interaction energy were of-11.92 kJ/mol.The formation of hydrogen bonds made the H―O stretching modes of complexes red-shifted relative to that of the monomer.At 298.15 K and standard state,the formations of stable complexes were an exothermic and non-spontaneous process.展开更多
The halogen and hydrogen bonding complexes and trihalomethanes （CHX3, X=C1, Br, I） are between 2,2,6,6-tetramethylpiperidine-noxyl simulated by computational quantum chem- istry. The molecular electrostatic potentia...The halogen and hydrogen bonding complexes and trihalomethanes （CHX3, X=C1, Br, I） are between 2,2,6,6-tetramethylpiperidine-noxyl simulated by computational quantum chem- istry. The molecular electrostatic potentials, geometrical parameters and interaction energy of halogen and hydrogen bonding complexes combined with natural bond orbital analysis are obtained. The results indicate that both halogen and hydrogen bonding interactions obey the order CI〈Br〈I, and hydrogen bonding is stronger than the corresponding halogen bond- ing. So, hydrogen bonding complexes should be dominant in trihalomethanes. However, it is possible that halogen bonding complex is competitive, even preponderant, in triiodomethane due to the similar interaction energy. This work might provide useful information on specific solvent effects as well as for understanding the mechanism of nitroxide radicals as a bioprobe to interact with the halogenated compounds in biological and biochemical fields.展开更多
The interaction between a gas molecule and photocatalyst is vital to trigger photocatalytic reaction.The surface state of photocatalyst affects much in this interaction.Herein,adsorption of H2O molecules on s-triazine...The interaction between a gas molecule and photocatalyst is vital to trigger photocatalytic reaction.The surface state of photocatalyst affects much in this interaction.Herein,adsorption of H2O molecules on s-triazine-based g-C3N4 was thoroughly studied by first-principle calculation.Although various initial adsorption models with multifarious locations of H2O molecules were built,the optimized models with strong adsorption energy pointed to the same adsorption configuration,in which the H2O molecule hold an upright orientation above the corrugated g-C3N4 monolayer.An intermolecular O-H…N hydrogen bond formed via the binding of a polar O-H bond in H2O molecule and a two-coordinated electron-rich nitrogen atom in g-C3N4.Under the bridging effect of this intermolecular hydrogen bond,electrons would transfer from g-C3N4 to the H2O molecule,thereby lowering the Fermi level and enlarging work function of g-C3N4.Interestingly,regardless of the substitute,i.e.g-C3N4 multilayer,large supercell and nanotube,this adsorption system was highly reproducible,as its geometry structure and electronic property remained unchanged.In addition,the effect of nonmetal element doping on adsorption energy was explored.This work not only disclosed a highly preferential H2O adsorbed g-C3N4 architecture established by intermolecular hydrogen bond,but also contributed to the deep understanding and optimized design in water-splitting process on g-C3N4-based photocatalysts.展开更多
The hydrogen bonding character between the BF4- and glycine was theoretically studied at the level of B3LYP/6-31＋G^＊, single point energies were performed at the level of B3LYP/6-311＋＋G^＊＊. The relevant geometri...The hydrogen bonding character between the BF4- and glycine was theoretically studied at the level of B3LYP/6-31＋G^＊, single point energies were performed at the level of B3LYP/6-311＋＋G^＊＊. The relevant geometrical characteristics, energy properties, as well as the characters of the intramolecular hydrogen bonds have been studied. Atoms in molecule theory topological analysis indicated the （3,-1） critical points for hydrogen bonds. In addition, the electron density and Laplacian were in the range suggested for the hydrogen bonds. Especially, the changes of atomic charge, hydrogen upon hydrogen bonds formation dipole moment, enegry as well as volume of the were systemitically discussed.展开更多
Carbon capture and storage technology have been rapidly developed to reduce the carbon dioxide(CO2)emission into the environment.It has been found that the amine-based organic molecules could absorb CO_(2) efficiently...Carbon capture and storage technology have been rapidly developed to reduce the carbon dioxide(CO2)emission into the environment.It has been found that the amine-based organic molecules could absorb CO_(2) efficiently and form the bicarbonate salts through hydrogen-bond(H-bond)interactions.Recently,the aqueous 1,3-diphenylguanidine(DPG)solution was developed to trap and convert CO_(2) to valuable chemicals under ambient conditions.However,how the DPG molecules interact with CO_(2) in an aqueous solution remains unclear.In this work,we perform molecular dynamics simulations to explore the atomistic details of CO_(2) in the aqueous DPG.The simulated results reveal that the protonated DPGH+and the bicarbonate anions prefer to form complexes through different H-bond patterns.These double H-bonds are quite stable in thermodynamics,as indicated from the accurate density functional theory calculations.This study is helpful to understand the catalytic mechanism of CO_(2) conversion in the aqueous DPG.展开更多
The interacting patterns and mechanism of the catechin and thymine have been investigated with the density functional theory Becke＇s three-parameter nonlocal exchange functional and the Lee, Yang, and Parr nonlocal c...The interacting patterns and mechanism of the catechin and thymine have been investigated with the density functional theory Becke＇s three-parameter nonlocal exchange functional and the Lee, Yang, and Parr nonlocal correlation functional （B3LYP） method by 6-31＋G＊ basis set. Thirteen stable structures for the catechin-thymine complexes have been found which form two hydrogen bonds at least. The vibrational frequencies are also studied at the same level to analyze these complexes. The results indicated that catechin interacted with thynfine by three different hydrogen bonds as N-H…O, C-H…O, O-H…O and the complexes are mainly stabilized by the hydrogen bonding interactions. Theories of atoms in molecules and natural bond orbital have been adopted to investigate the hydrogen bonds involved in all systems. The interaction energies of all complexes have been corrected for basis set superposition error, which are from -18.15 k J/mol to -32.99 kJ/mol. The results showed that the hydrogen bonding contribute to the interaction energies dominantly. The corresponding bonds stretching motions in all complexes are red-shifted relative to that of the inonomer, which is in agreement with experimental results.展开更多
The depletion potential between two colloid particles immersed in a hydrogen bonding fluid has been investigated by density functional theory. The study is motivated by the wide applications of hydrogen bonding fluids...The depletion potential between two colloid particles immersed in a hydrogen bonding fluid has been investigated by density functional theory. The study is motivated by the wide applications of hydrogen bonding fluids in the field of colloid science, and the effects of relevant factors on the depletion potential and depletion force between colloid particles have been studied. These factors include the size ratio of the colloid particle to the fluid molecule, the bulk density of the fluid, the functionality (the number of proton acceptors a and proton donors d) and hydrogen bonding strength as well as the colloid-fluid interaction energy. By comparing the depletion potential calculated under various conditions, it is shown that the effects of these factors on the depletion potential are very significant, and in particular in regulating the depletion force and its range.展开更多
The interacting patterns and mechanism of the catechin and cytosine have been investigated using the density functional theory B3LYP method with 6-31+G* basis set.Eleven stable structures of the catechin-cytosine comp...The interacting patterns and mechanism of the catechin and cytosine have been investigated using the density functional theory B3LYP method with 6-31+G* basis set.Eleven stable structures of the catechin-cytosine complexes have been found respectively.The results indicate that the complexes are mainly stabilized by the hydrogen bonding interactions.Theories of atoms in molecules(AIM) and natural bond orbital(NBO) have been utilized to investigate the hydrogen bonds involved in all the systems.The interaction energies of all the complexes which were corrected for basis set superposition error(BSSE),are from-17.35 to-43.27 kJ/mol.The results show that the hydrogen bonding contributes to the interaction energies dominantly.The corresponding bonds stretching motions in all the complexes are red-shifted relative to that of the monomer,which is in good agreement with experimental results.展开更多
Halogen bonding interactions between several halogenated ion pairs and CO2 molecules have been investigated by means of density functional theory calculations. To account for the influence of solvent environment, the ...Halogen bonding interactions between several halogenated ion pairs and CO2 molecules have been investigated by means of density functional theory calculations. To account for the influence of solvent environment, the implicit polarized continuum model was also employed. The bromide and iodide cations of ionic liquids (ILs) under study can interact with CO2 molecules via X O interactions, which become much stronger in strength than those in the complexes of iodo-perfluorobenzenes, very effective halogen bond donors, with CO2 molecules. Such interactions, albeit somewhat weaker in strength, are also observed between halogenated ion pairs and CO2 molecules. Thus, the solubility of CO2 may be improved when using halogenated ILs, as a result of the formation of X O halogen bonds. Under solvent effects, the strength of the interactions tends to be weakened to some degree, with a concomitant elongation of intermolecular distances. The results presented here would be very useful in the design and synthesis of novel and potent ILs for CO2 physical absorption.展开更多
基金Supported by Key Natural Science Program of the Education Department of Sichuan Province(07ZB080)Scientific Research Foundation for Masters of Xichang College~~
文摘B3LYP/6-311＋＋G level were employed to obtain the optimized geometries and calculated frequency of HCOCl and HOCl complexes.Five stable isomers were obtained,and the one with ClO-H…O=C hydrogen bond was the most stable among five stable isomers,the BSSE and ZPE corrected interaction energy were of-11.92 kJ/mol.The formation of hydrogen bonds made the H―O stretching modes of complexes red-shifted relative to that of the monomer.At 298.15 K and standard state,the formations of stable complexes were an exothermic and non-spontaneous process.
基金This work is supported by the National Natural Science Foundation of China （No.20675009 and No.90922023） and the Research Fund for the Doctoral Program of Higher Education of China （No.273914）.
文摘The halogen and hydrogen bonding complexes and trihalomethanes （CHX3, X=C1, Br, I） are between 2,2,6,6-tetramethylpiperidine-noxyl simulated by computational quantum chem- istry. The molecular electrostatic potentials, geometrical parameters and interaction energy of halogen and hydrogen bonding complexes combined with natural bond orbital analysis are obtained. The results indicate that both halogen and hydrogen bonding interactions obey the order CI〈Br〈I, and hydrogen bonding is stronger than the corresponding halogen bond- ing. So, hydrogen bonding complexes should be dominant in trihalomethanes. However, it is possible that halogen bonding complex is competitive, even preponderant, in triiodomethane due to the similar interaction energy. This work might provide useful information on specific solvent effects as well as for understanding the mechanism of nitroxide radicals as a bioprobe to interact with the halogenated compounds in biological and biochemical fields.
文摘The interaction between a gas molecule and photocatalyst is vital to trigger photocatalytic reaction.The surface state of photocatalyst affects much in this interaction.Herein,adsorption of H2O molecules on s-triazine-based g-C3N4 was thoroughly studied by first-principle calculation.Although various initial adsorption models with multifarious locations of H2O molecules were built,the optimized models with strong adsorption energy pointed to the same adsorption configuration,in which the H2O molecule hold an upright orientation above the corrugated g-C3N4 monolayer.An intermolecular O-H…N hydrogen bond formed via the binding of a polar O-H bond in H2O molecule and a two-coordinated electron-rich nitrogen atom in g-C3N4.Under the bridging effect of this intermolecular hydrogen bond,electrons would transfer from g-C3N4 to the H2O molecule,thereby lowering the Fermi level and enlarging work function of g-C3N4.Interestingly,regardless of the substitute,i.e.g-C3N4 multilayer,large supercell and nanotube,this adsorption system was highly reproducible,as its geometry structure and electronic property remained unchanged.In addition,the effect of nonmetal element doping on adsorption energy was explored.This work not only disclosed a highly preferential H2O adsorbed g-C3N4 architecture established by intermolecular hydrogen bond,but also contributed to the deep understanding and optimized design in water-splitting process on g-C3N4-based photocatalysts.
文摘The hydrogen bonding character between the BF4- and glycine was theoretically studied at the level of B3LYP/6-31＋G^＊, single point energies were performed at the level of B3LYP/6-311＋＋G^＊＊. The relevant geometrical characteristics, energy properties, as well as the characters of the intramolecular hydrogen bonds have been studied. Atoms in molecule theory topological analysis indicated the （3,-1） critical points for hydrogen bonds. In addition, the electron density and Laplacian were in the range suggested for the hydrogen bonds. Especially, the changes of atomic charge, hydrogen upon hydrogen bonds formation dipole moment, enegry as well as volume of the were systemitically discussed.
基金supported by the National Natural Science Foundation of China(No.21973015 and No.22125301)。
文摘Carbon capture and storage technology have been rapidly developed to reduce the carbon dioxide(CO2)emission into the environment.It has been found that the amine-based organic molecules could absorb CO_(2) efficiently and form the bicarbonate salts through hydrogen-bond(H-bond)interactions.Recently,the aqueous 1,3-diphenylguanidine(DPG)solution was developed to trap and convert CO_(2) to valuable chemicals under ambient conditions.However,how the DPG molecules interact with CO_(2) in an aqueous solution remains unclear.In this work,we perform molecular dynamics simulations to explore the atomistic details of CO_(2) in the aqueous DPG.The simulated results reveal that the protonated DPGH+and the bicarbonate anions prefer to form complexes through different H-bond patterns.These double H-bonds are quite stable in thermodynamics,as indicated from the accurate density functional theory calculations.This study is helpful to understand the catalytic mechanism of CO_(2) conversion in the aqueous DPG.
文摘The interacting patterns and mechanism of the catechin and thymine have been investigated with the density functional theory Becke＇s three-parameter nonlocal exchange functional and the Lee, Yang, and Parr nonlocal correlation functional （B3LYP） method by 6-31＋G＊ basis set. Thirteen stable structures for the catechin-thymine complexes have been found which form two hydrogen bonds at least. The vibrational frequencies are also studied at the same level to analyze these complexes. The results indicated that catechin interacted with thynfine by three different hydrogen bonds as N-H…O, C-H…O, O-H…O and the complexes are mainly stabilized by the hydrogen bonding interactions. Theories of atoms in molecules and natural bond orbital have been adopted to investigate the hydrogen bonds involved in all systems. The interaction energies of all complexes have been corrected for basis set superposition error, which are from -18.15 k J/mol to -32.99 kJ/mol. The results showed that the hydrogen bonding contribute to the interaction energies dominantly. The corresponding bonds stretching motions in all complexes are red-shifted relative to that of the inonomer, which is in agreement with experimental results.
基金supported by the National Natural Science Foundation of China (20873035)
文摘The depletion potential between two colloid particles immersed in a hydrogen bonding fluid has been investigated by density functional theory. The study is motivated by the wide applications of hydrogen bonding fluids in the field of colloid science, and the effects of relevant factors on the depletion potential and depletion force between colloid particles have been studied. These factors include the size ratio of the colloid particle to the fluid molecule, the bulk density of the fluid, the functionality (the number of proton acceptors a and proton donors d) and hydrogen bonding strength as well as the colloid-fluid interaction energy. By comparing the depletion potential calculated under various conditions, it is shown that the effects of these factors on the depletion potential are very significant, and in particular in regulating the depletion force and its range.
基金supported by the National Natural Science Foundation of China (30870257)
文摘The interacting patterns and mechanism of the catechin and cytosine have been investigated using the density functional theory B3LYP method with 6-31+G* basis set.Eleven stable structures of the catechin-cytosine complexes have been found respectively.The results indicate that the complexes are mainly stabilized by the hydrogen bonding interactions.Theories of atoms in molecules(AIM) and natural bond orbital(NBO) have been utilized to investigate the hydrogen bonds involved in all the systems.The interaction energies of all the complexes which were corrected for basis set superposition error(BSSE),are from-17.35 to-43.27 kJ/mol.The results show that the hydrogen bonding contributes to the interaction energies dominantly.The corresponding bonds stretching motions in all the complexes are red-shifted relative to that of the monomer,which is in good agreement with experimental results.
基金supported by the National Basic Research Program of China (2009CB219902)the Natural Science Foundation of Shanghai (11ZR1408700)the National Natural Science Foundation of China (21136004 and 21103047)
文摘Halogen bonding interactions between several halogenated ion pairs and CO2 molecules have been investigated by means of density functional theory calculations. To account for the influence of solvent environment, the implicit polarized continuum model was also employed. The bromide and iodide cations of ionic liquids (ILs) under study can interact with CO2 molecules via X O interactions, which become much stronger in strength than those in the complexes of iodo-perfluorobenzenes, very effective halogen bond donors, with CO2 molecules. Such interactions, albeit somewhat weaker in strength, are also observed between halogenated ion pairs and CO2 molecules. Thus, the solubility of CO2 may be improved when using halogenated ILs, as a result of the formation of X O halogen bonds. Under solvent effects, the strength of the interactions tends to be weakened to some degree, with a concomitant elongation of intermolecular distances. The results presented here would be very useful in the design and synthesis of novel and potent ILs for CO2 physical absorption.
