The non-additivity of the methyl groups in the single-electron lithium bond was investigated using ab initio calculations at the B3LYP/6-311＋＋G＊＊ and UMP2/6-311＋＋G＊＊ levels. The strength of the interaction in ...The non-additivity of the methyl groups in the single-electron lithium bond was investigated using ab initio calculations at the B3LYP/6-311＋＋G＊＊ and UMP2/6-311＋＋G＊＊ levels. The strength of the interaction in the H3C… LiH, H3CH2C… LiH, （H3C）2HC… LiH, and u v （H3C）3C… LiH complexes was analyzed in term of the geometries, energies, frequency shifts, stabilization energies, charges, and topological parameters. It is shown that （H3C）3C radical with LiH forms the strongest single-electron lithium bond, followed by （H3C）2HC radical, then H3CH2C radical, and H3C radical forms the weakest single-electron lithium bond. A positive non-additivity is present among methyl groups. Natural bond orbital and atoms in molecules analyses were used to estimate such conclusions. Furthermore, there are few linear/nonlinear relationships in the system and the interaction mode of single-electron Li- bond is different from the single-electron H-bond and single-electron halogen bond.展开更多
The results of predicting thermodynamic properties in the full composition range of Ti-Al binary melts in a temperature range from 1973 to 2273 K were obtained by coupling with the developed thermodynamic model for ca...The results of predicting thermodynamic properties in the full composition range of Ti-Al binary melts in a temperature range from 1973 to 2273 K were obtained by coupling with the developed thermodynamic model for calculating mass action concentration N_i of structural units in Ti-Al system based on the atom and molecule coexistence theory（AMCT）. Temperature dependence of the activity coefficients of Ti and Al in natural logarithmic form in the infinitely dilute solution（0x_（Ti）0.01） of Ti-Al binary melts was also determined from the calculated activity coefficients of Ti and Al at temperatures of 1973, 2073, 2173, and 2273 K. The standard molar Gibbs free energy change of dissolving pure liquid element i（l） for forming 1%（mass fraction） element i in Ti-Al binary melts further was deduced. With the aid of this model, meanwhile, the determined excess thermodynamic properties, such as the excess molar mixing Gibbs free energy/entropy/enthalpy were also calculated.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
A perturbation theory model that describes splitting of the spectra in highly symmetrical molecular species in electrostatic field is proposed. An anahrmonie model of a two-dimensional oscillator having Kratzer potent...A perturbation theory model that describes splitting of the spectra in highly symmetrical molecular species in electrostatic field is proposed. An anahrmonie model of a two-dimensional oscillator having Kratzer potential energy function is used to model the molecular species and to represent the unperturbed system. A selection rule for the radial quantum number of the oscillator is derived. The eigenfunctions of a two-dimensional anharmonic oscillator in cylindrical coordinates are used for the matrix elements representing the probability for energy transitions in dipole approximation to be calculated. Several forms of perturbation operators are proposed to model the interaction between the polyatomic molecular species and an electrostatic field. It is found that the degeneracy is removed in the presence of the electric field and spectral splitting occurs. Anharmonic approximation for the unperturbed system is more accurate and reliable representation of a reaJ polyatomic molecular species.展开更多
The formation mechanism for the regular octahedral structure of Liscluster is proposed. The curve of the total energy versus the separation R between any two neighboring nuclei has been calculated by using the method ...The formation mechanism for the regular octahedral structure of Liscluster is proposed. The curve of the total energy versus the separation R between any two neighboring nuclei has been calculated by using the method of Gou＇s modified arrangement channel quantum mechanics （MACQM）. The result shows that the curve has a minimal energy of -44.736 89 a.u. at R = 5.07a0. When R approaches infinity, the total energy of six lithium atoms has the value of -44.568 17 a.u. So the binding energy of Li6 with respect to six lithium atoms is 0.1687 a.u. Therefore, the binding energy per atom for Li6 is 0.028 12 a.u., or 0.7637 eV, which is greater than the binding energy per atom of 0.453 eV for Li2 and the binding energy per atom of 0.494 eV for Li3 calculated in our previous work. This means that the Li6 cluster may be formed in a regular octahedral structure with a greater binding energy.展开更多
The structure and stability of the compounds MRg^(+)and MRg F(Rg=Ar,Kr,and Xe;M=Co,Rh,and Ir)were investigated using the B3 LYP,MP2,MP4(SDQ)and CCSD(T)methods.We reported the geometry,vibrational frequencies and therm...The structure and stability of the compounds MRg^(+)and MRg F(Rg=Ar,Kr,and Xe;M=Co,Rh,and Ir)were investigated using the B3 LYP,MP2,MP4(SDQ)and CCSD(T)methods.We reported the geometry,vibrational frequencies and thermodynamics properties of these compounds.A series of theoretical methods on the basis of wavefunction analysis,including natural bond orbitals,atoms in molecules,electron localization function,and energy decomposition analysis,were performed to explore bonding nature of the M-Rg and Rg-F bonds.These bonds are mainly noncovalent,the metal weakly interacts with Rg in MRg^(+),but their interaction is much stronger in MRg F.The neutral molecule MRg F can be well described by the Lewis structure[MRg]^(+)F^(-).展开更多
We study the normal form of multipartite density matrices.It is shown that the correlation matrix(CM)separability criterion can be improved from the normal form we obtained under filtering transformations.Based on CMc...We study the normal form of multipartite density matrices.It is shown that the correlation matrix(CM)separability criterion can be improved from the normal form we obtained under filtering transformations.Based on CMcriterion the entanglement witness is further constructed in terms of local orthogonal observables for both bipartite andmultipartite systems.展开更多
The theory of generalized Besov-Morrey spaces and generalized Triebel-Lizorkin-Morrey spaces is developed. Generalized Morrey spaces, which Mizuhara and Nakai proposed, are equipped with a parameter and a function. Th...The theory of generalized Besov-Morrey spaces and generalized Triebel-Lizorkin-Morrey spaces is developed. Generalized Morrey spaces, which Mizuhara and Nakai proposed, are equipped with a parameter and a function. The trace property is one of the main focuses of the present paper, which will clarify the role of the parameter of generalized Morrey spaces. The quarkonial decomposition is obtained as an application of the atomic decomposition. In the end, the relation between the function spaces dealt in the present paper and the foregoing researches is discussed.展开更多
Above-threshold ionizations of rare gas atoms excited by polarized femtosecond laser pulses are investigated.The photoelectron momentum spectra are obtained applying the strong-field approximation(SFA) theory.It is fo...Above-threshold ionizations of rare gas atoms excited by polarized femtosecond laser pulses are investigated.The photoelectron momentum spectra are obtained applying the strong-field approximation(SFA) theory.It is found that,distribution of the emitted photoelectrons varies with different polarizations of laser pulses.We have interpreted the relationship between the observed distribution and the laser polarization taking advantage of tunneling ionization theory and simple-man model.The polarization sensitivity indicates that one can easily manipulate the photoelectron distribution by controlling the polarization of the exciting pulse.展开更多
This paper is proposed to understand the interaction of porphyrin layers with diatomic molecules interacting at their interior regions by applying ab initio and density functional theory （DFT） methods. We have used ...This paper is proposed to understand the interaction of porphyrin layers with diatomic molecules interacting at their interior regions by applying ab initio and density functional theory （DFT） methods. We have used NO, GO, and O2 diatomic molecules to interact with the porphyrin layers. The most common Fe-centered metalloporphyrin structure with tetra-pyrrlic rings having N4 core is chosen for the study. The optimization of Porphyrin-Porphyrin （PI-PII） and Porphyrin-Diatomic molecule-Porphyrin （P1-AB-P11） （AB = NO, CO, and 02） complexes are performed using HF method. In order to understand the planarity and appropriate stacking size of porphyrins and also to infer the separation of diatomic molecules between porphyrin layers the behavior of PI-AB-PH complexes （where AB = NO, CO, and 02） are analyzed using structural properties and molecular electrostatic potentials （MEP）. The MEPs are caiculated using hybrid exchange correlation functional B3PW91 of DFT Mong with 6-31＋G basis set for the PI-PH and PI-AB-Pzz complexes obtained from HF method.展开更多
A recently developed B-spline algorithm is extended and utilized to calculate excited states of He atoms in the presence of strong magnetic fields.Binding energies are presented for He in the five excited atomic state...A recently developed B-spline algorithm is extended and utilized to calculate excited states of He atoms in the presence of strong magnetic fields.Binding energies are presented for He in the five excited atomic states 210-+,110-,210-,11(-1)+,and 2 1(1) + with magnetic field strength ranging from 0.0001 to 10 a.u.The obtained energies are compared with available theoretical data,and found to be in good agreement.We investigate influence of magnetic fields on atomic structures of multielectron atoms,and illustrate that how electron probability density distributions change with increasing magnetic field strength.The current approach is directly applicable to simulations of discrete spectra for He atoms in the atmospheres of magnetized white dwarf stars.展开更多
文摘The non-additivity of the methyl groups in the single-electron lithium bond was investigated using ab initio calculations at the B3LYP/6-311＋＋G＊＊ and UMP2/6-311＋＋G＊＊ levels. The strength of the interaction in the H3C… LiH, H3CH2C… LiH, （H3C）2HC… LiH, and u v （H3C）3C… LiH complexes was analyzed in term of the geometries, energies, frequency shifts, stabilization energies, charges, and topological parameters. It is shown that （H3C）3C radical with LiH forms the strongest single-electron lithium bond, followed by （H3C）2HC radical, then H3CH2C radical, and H3C radical forms the weakest single-electron lithium bond. A positive non-additivity is present among methyl groups. Natural bond orbital and atoms in molecules analyses were used to estimate such conclusions. Furthermore, there are few linear/nonlinear relationships in the system and the interaction mode of single-electron Li- bond is different from the single-electron H-bond and single-electron halogen bond.
基金Project(U1560203)supported by the Joint Funds of the National Natural Science Foundation of ChinaProject(51274031)supported by the National Natural Science Foundation of China
文摘The results of predicting thermodynamic properties in the full composition range of Ti-Al binary melts in a temperature range from 1973 to 2273 K were obtained by coupling with the developed thermodynamic model for calculating mass action concentration N_i of structural units in Ti-Al system based on the atom and molecule coexistence theory（AMCT）. Temperature dependence of the activity coefficients of Ti and Al in natural logarithmic form in the infinitely dilute solution（0x_（Ti）0.01） of Ti-Al binary melts was also determined from the calculated activity coefficients of Ti and Al at temperatures of 1973, 2073, 2173, and 2273 K. The standard molar Gibbs free energy change of dissolving pure liquid element i（l） for forming 1%（mass fraction） element i in Ti-Al binary melts further was deduced. With the aid of this model, meanwhile, the determined excess thermodynamic properties, such as the excess molar mixing Gibbs free energy/entropy/enthalpy were also calculated.
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.
文摘A perturbation theory model that describes splitting of the spectra in highly symmetrical molecular species in electrostatic field is proposed. An anahrmonie model of a two-dimensional oscillator having Kratzer potential energy function is used to model the molecular species and to represent the unperturbed system. A selection rule for the radial quantum number of the oscillator is derived. The eigenfunctions of a two-dimensional anharmonic oscillator in cylindrical coordinates are used for the matrix elements representing the probability for energy transitions in dipole approximation to be calculated. Several forms of perturbation operators are proposed to model the interaction between the polyatomic molecular species and an electrostatic field. It is found that the degeneracy is removed in the presence of the electric field and spectral splitting occurs. Anharmonic approximation for the unperturbed system is more accurate and reliable representation of a reaJ polyatomic molecular species.
基金National Natural Science Foundation of China under Grant No.19974027
文摘The formation mechanism for the regular octahedral structure of Liscluster is proposed. The curve of the total energy versus the separation R between any two neighboring nuclei has been calculated by using the method of Gou＇s modified arrangement channel quantum mechanics （MACQM）. The result shows that the curve has a minimal energy of -44.736 89 a.u. at R = 5.07a0. When R approaches infinity, the total energy of six lithium atoms has the value of -44.568 17 a.u. So the binding energy of Li6 with respect to six lithium atoms is 0.1687 a.u. Therefore, the binding energy per atom for Li6 is 0.028 12 a.u., or 0.7637 eV, which is greater than the binding energy per atom of 0.453 eV for Li2 and the binding energy per atom of 0.494 eV for Li3 calculated in our previous work. This means that the Li6 cluster may be formed in a regular octahedral structure with a greater binding energy.
文摘The structure and stability of the compounds MRg^(+)and MRg F(Rg=Ar,Kr,and Xe;M=Co,Rh,and Ir)were investigated using the B3 LYP,MP2,MP4(SDQ)and CCSD(T)methods.We reported the geometry,vibrational frequencies and thermodynamics properties of these compounds.A series of theoretical methods on the basis of wavefunction analysis,including natural bond orbitals,atoms in molecules,electron localization function,and energy decomposition analysis,were performed to explore bonding nature of the M-Rg and Rg-F bonds.These bonds are mainly noncovalent,the metal weakly interacts with Rg in MRg^(+),but their interaction is much stronger in MRg F.The neutral molecule MRg F can be well described by the Lewis structure[MRg]^(+)F^(-).
基金National Natural Science Foundation of China under Grant Nos.10675086 and KM200510028022National Key Basic Research Program of China under Grant No.2004CB318000
文摘We study the normal form of multipartite density matrices.It is shown that the correlation matrix(CM)separability criterion can be improved from the normal form we obtained under filtering transformations.Based on CMcriterion the entanglement witness is further constructed in terms of local orthogonal observables for both bipartite andmultipartite systems.
文摘The theory of generalized Besov-Morrey spaces and generalized Triebel-Lizorkin-Morrey spaces is developed. Generalized Morrey spaces, which Mizuhara and Nakai proposed, are equipped with a parameter and a function. The trace property is one of the main focuses of the present paper, which will clarify the role of the parameter of generalized Morrey spaces. The quarkonial decomposition is obtained as an application of the atomic decomposition. In the end, the relation between the function spaces dealt in the present paper and the foregoing researches is discussed.
基金Supported by the National Natural Science Foundation of China under Grant No. 11104210
文摘Above-threshold ionizations of rare gas atoms excited by polarized femtosecond laser pulses are investigated.The photoelectron momentum spectra are obtained applying the strong-field approximation(SFA) theory.It is found that,distribution of the emitted photoelectrons varies with different polarizations of laser pulses.We have interpreted the relationship between the observed distribution and the laser polarization taking advantage of tunneling ionization theory and simple-man model.The polarization sensitivity indicates that one can easily manipulate the photoelectron distribution by controlling the polarization of the exciting pulse.
基金the Science and Engineering Research Board (SERB), India for awarding the fast track project (Project No: SB/FTP/PS-096/2013)
文摘This paper is proposed to understand the interaction of porphyrin layers with diatomic molecules interacting at their interior regions by applying ab initio and density functional theory （DFT） methods. We have used NO, GO, and O2 diatomic molecules to interact with the porphyrin layers. The most common Fe-centered metalloporphyrin structure with tetra-pyrrlic rings having N4 core is chosen for the study. The optimization of Porphyrin-Porphyrin （PI-PII） and Porphyrin-Diatomic molecule-Porphyrin （P1-AB-P11） （AB = NO, CO, and 02） complexes are performed using HF method. In order to understand the planarity and appropriate stacking size of porphyrins and also to infer the separation of diatomic molecules between porphyrin layers the behavior of PI-AB-PH complexes （where AB = NO, CO, and 02） are analyzed using structural properties and molecular electrostatic potentials （MEP）. The MEPs are caiculated using hybrid exchange correlation functional B3PW91 of DFT Mong with 6-31＋G basis set for the PI-PH and PI-AB-Pzz complexes obtained from HF method.
基金Supported by the National Science Foundation of USA under Grant No. 0630370National Natural Science Foundation of Chinaunder Grant Nos. 90403028 and 11074260
文摘A recently developed B-spline algorithm is extended and utilized to calculate excited states of He atoms in the presence of strong magnetic fields.Binding energies are presented for He in the five excited atomic states 210-+,110-,210-,11(-1)+,and 2 1(1) + with magnetic field strength ranging from 0.0001 to 10 a.u.The obtained energies are compared with available theoretical data,and found to be in good agreement.We investigate influence of magnetic fields on atomic structures of multielectron atoms,and illustrate that how electron probability density distributions change with increasing magnetic field strength.The current approach is directly applicable to simulations of discrete spectra for He atoms in the atmospheres of magnetized white dwarf stars.
