The lowest energy structures of peroxynitric acid have been studied with B3LYP/6-311＋ G（2d,2p） method. The potential energy surfaces （PES） along the O-N and O-O bonds have been scanned at CCSD（T）/aug-cc-pVDZ le...The lowest energy structures of peroxynitric acid have been studied with B3LYP/6-311＋ G（2d,2p） method. The potential energy surfaces （PES） along the O-N and O-O bonds have been scanned at CCSD（T）/aug-cc-pVDZ level, respectively. The calculated results show that on the O-N PES, the O3-N4 bond length of the loose transition state is 2.82A^° and the corresponding energy barrier is 25.6 kcal/mol, while on the O-O PES, the loose transition state with of O2-O3 bond length of 2.35A^° has the energy barrier of 37.4 kcal/mol. Thus the primary reaction path for peroxynitric acid is the dissociation into HO2 and NO2.展开更多
Using density functional theory and polarizable continuum models, we study the Raman spectra of aqueous peroxynitric acid. The calculated results indicate that the solvent effect has significant influence on the elect...Using density functional theory and polarizable continuum models, we study the Raman spectra of aqueous peroxynitric acid. The calculated results indicate that the solvent effect has significant influence on the electric dipole transition moments between the ground and excited electronic state and Raman polarizabilities. The theoretical Raman spectra agree well with the experimental results. From the experimental depolarization ratio, we can conclude that peroxynitric acid is not a plane molecule. We also find that the hydrogen bond can enhance IR intensity of hydroxyl group by several times.展开更多
This article described the characteristics of the liquid nitrogen engine's ideal open cycle.Using two interconnecting strokes to achieve the power output can mitigate the trade-off between high efficiency and the ...This article described the characteristics of the liquid nitrogen engine's ideal open cycle.Using two interconnecting strokes to achieve the power output can mitigate the trade-off between high efficiency and the potential mechanical complexity of multiple-cylinder engines. The total specific energy of the binary media (methane-nitrogen) cycle system could be much higher than the unitary medium (liquid nitrogen) cycle system. By theoretical analysis, the reasonably acceptable driving range proved the feasibility of the liquid nitrogen engine used for supplying power for a lightweight car.展开更多
The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by the...The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving a-COOH or b-COOH group had energy barriers of DE = 58.67 kJmol-1 and 103.94 kJmol-1, respectively. These results were in agreement with the experimental data. So the a-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not b-COOH group.展开更多
The reaction mechanism of PCl3/H2 on silicon substrate surface （simulated by Si4 cluster） was investigated with Density Functional Theory （DFT） at the B3LYP/6-311G^＊＊ level. On silicon substrate, PCl3 firstly un...The reaction mechanism of PCl3/H2 on silicon substrate surface （simulated by Si4 cluster） was investigated with Density Functional Theory （DFT） at the B3LYP/6-311G^＊＊ level. On silicon substrate, PCl3 firstly undergoes dissociative adsorption, and then the adsorption product reacts with H2 via a four-step multi-channel mode to give the final product PSi4 cluster. The geometries at each stationary point were fully optimized. The possible transition states were determined by vibrational mode analysis and IRC verification. And finally, the main reaction channel was given.展开更多
Two Pb^Ⅱ coordination polymers [Pb（oba）（2,2′-bipy）]·1.5H2O（1） and [Pb（oba）（phen）]（2）（H2oba = 2,4-oxybis（benzoic acid）, 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline） were synthesized...Two Pb^Ⅱ coordination polymers [Pb（oba）（2,2′-bipy）]·1.5H2O（1） and [Pb（oba）（phen）]（2）（H2oba = 2,4-oxybis（benzoic acid）, 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline） were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. Structures of compounds 1 and 2 are similar. Compounds 1 and 2 show 1D wavy chains, which are further connected through aromatic π-π stacking interactions to expand into 2D wavelike networks. The crystal structure of 2,4-oxybis（benzoic acid） ligand（3） was obtained, and its full geometry optimization was carried out by using DFT methods at the B3LYP/6-31G（d） level. The calculated data show that the bond distances and bond angles were very close to the experimental data. The values of the frontier orbital energies indicate that this configuration is stable. Moreover, the solid-state fluorescence properties of 1-3 have also been investigated.展开更多
An accurate theoretical study on the MgH radical is reported by adopting the high-level relativistic MRCI＋Q method with a quintuple-zeta quality basis set. The reliable potential energy curves of the five A-S states ...An accurate theoretical study on the MgH radical is reported by adopting the high-level relativistic MRCI＋Q method with a quintuple-zeta quality basis set. The reliable potential energy curves of the five A-S states of MgH are derived. Then the associated spectroscopic parameters are determined and found to be in good accordance with the available experimental results. The permanent dipole moments （PDMs） and the spin-orbit （SO） matrix elements of A-S states are computed. The results show that the abrupt changes of PDMs and SO matrix elements are attributed to the variations of electronic configurations at the avoided crossing point. The SOC effect leads to the five A-S states split into ten Ω states and results in the double potential well of （2）1//2 state. Finally, the transition properties from the （2）1//2, （1）3//2 and （3）1//2 states to the ground state X2∑＋1//2 transitions are obtained, including the transition dipole moments, Franck-Condon factors and radiative lifetimes.展开更多
The carrier mobility of two-dimensional tetragonal carbon allotrope （T-CA） from porous graphene is investigated by first-principles calculations. T-CA can be constructed from divacancy and Stone-Thrower--Wales defec...The carrier mobility of two-dimensional tetragonal carbon allotrope （T-CA） from porous graphene is investigated by first-principles calculations. T-CA can be constructed from divacancy and Stone-Thrower--Wales defects from graphene. T-CA is a direct semiconductor with a band gap of 0.4 eV at F point. T-CA possesses a high carrier mobility of the order of 104 cm2V-ls-1. As our study demonstrates, T-CA has potential applications for next-generation electronic materials.展开更多
The mechanism and kinetics for the decomposition of 3-hydroxy-3-methyl-2-butanone have been studied by using the ab initio RHF/3-21G method. The calculated activation barrier of the reaction is 249.6kJ/mol which is in...The mechanism and kinetics for the decomposition of 3-hydroxy-3-methyl-2-butanone have been studied by using the ab initio RHF/3-21G method. The calculated activation barrier of the reaction is 249.6kJ/mol which is in reasonable agreement with the experimental data (222.2±3kJ/mol). The calculated results show that the decomposition is a concerted process with hydrogen transferring and bond breaking via a five-membered cyclic transition state. The thermal rate constants of the decomposition are obtained by calculating microcanonical probability fluxes through transition state1.展开更多
The reaction mechanism between CC12 and armchair single-walled carbon nanotubes （ASWCNTs） （3,3） and （4,4） has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CC12 adding to AS...The reaction mechanism between CC12 and armchair single-walled carbon nanotubes （ASWCNTs） （3,3） and （4,4） has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CC12 adding to ASWCNT （3,3） and （4,4） are computed and compared. The lower barrier of CC12 forms cycloaddition isomer on （3,3） maybe because the strain energy of （3,3） is larger than that of （4,4）. Our theoretical results are consistent with the experimental results.展开更多
The reaction of Au＋（1S,3D） with CS2 has been investigated at the B3LYP and CCSD（T） levels of theory.The identified reaction pathways revealed that the experimentally observed products,AuS＋ and AuCS＋,can be prod...The reaction of Au＋（1S,3D） with CS2 has been investigated at the B3LYP and CCSD（T） levels of theory.The identified reaction pathways revealed that the experimentally observed products,AuS＋ and AuCS＋,can be produced by the insertion of Au＋ into C-S bond.The calculated energetics shows that the reactions on singlet surface lead to excited-state products,AuS＋（1Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 1S,and have notable energy barriers,whereas the reactions on triplet surface producing the ground state products of AuS＋（3Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 3S are energetically much more favorable.This result suggests that the minor formations of AuS＋ and AuCS＋ observed in the previous experiment under room-temperature condition should result from the reactions of excited-state Au＋（3D） with CS2.Further,the possibility for singlet-triplet surface crossing was also discussed by approximately determining the crossing region.展开更多
Semi-empirical method PM3 was used to study the geometry and vibrational spectrum of N-(2-hydroxy-l-naphthyl-methylene)-l-pyrenamine (NPY) with the intermediate hydrogen bond. Results are comparable to experimentation...Semi-empirical method PM3 was used to study the geometry and vibrational spectrum of N-(2-hydroxy-l-naphthyl-methylene)-l-pyrenamine (NPY) with the intermediate hydrogen bond. Results are comparable to experimentations. Based on results of both NPY and its model, N-(2-hydroxy-l-naphthyl-methylene)aniline, it was found that the N-(2-hydroxy-l-naphthyl-methylene) group is principally responsible for the special hydrogen bonding through conjugation effect.展开更多
We compute the thermodynamic and the kinetic properties for the reaction: HCOCN→HCH+CO using the statistical theory and the transition-state theory.The equi- librium constants and the rate coefficients of this reacti...We compute the thermodynamic and the kinetic properties for the reaction: HCOCN→HCH+CO using the statistical theory and the transition-state theory.The equi- librium constants and the rate coefficients of this reaction are also reported here,and the half lives of formyl cyanide at different temperatures are first estimated in this work.展开更多
The geometries and vibrational frequencies of the ground and low-lying excited states for B_3, B_3^- and B_3^+ are determined with the energy gradient method using the polarized double-zeta(6-31G*) basis set. The stab...The geometries and vibrational frequencies of the ground and low-lying excited states for B_3, B_3^- and B_3^+ are determined with the energy gradient method using the polarized double-zeta(6-31G*) basis set. The stabilities for the states of B_3,B_3^- and B_3^+ have been investigated based on the vibrational analysis. The correlation energy obtained for each state is considered with the configuration interaction (CISD+Q) technique. B_3 and B_3^+ have stable equilateral triangle geometry, while B_3^- has stable equilateral triangle, isosceles triangle and linear geometries. The Jahn-Teller distortion for a ~3E' state of B_3^- in D_(3h) symmetry is also discussed.展开更多
Molecular structures, reorganization energies and charge transport matrix elements of coronene and its fluoro-, hydroxyl- and sulfhydryl-substituted derivatives have been studied at the B3LYP/6-31G＊＊ level. Based on...Molecular structures, reorganization energies and charge transport matrix elements of coronene and its fluoro-, hydroxyl- and sulfhydryl-substituted derivatives have been studied at the B3LYP/6-31G＊＊ level. Based on the semi-classical model of electron transfer, charge transport rate constants of the title molecules have been calculated. The results indicate that the coronene molecule is helpful to the transport of negative charge, and the transport rate of positive charge is between those of hexaazatriphenylene and triphenylene.展开更多
The intermolecular clusters of sulfur dioxide with water, SO2（H2O）n （n = 2～5）, are studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets （6-311＋＋G（d,p） an...The intermolecular clusters of sulfur dioxide with water, SO2（H2O）n （n = 2～5）, are studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets （6-311＋＋G（d,p） and aug-cc-pVDZ）. The equilibrium geometries, intermolecular binding energies, and anharmonic frequencies of the clusters are calculated and compared with those of pure water clusters and available experiments. SO2 tends to form cyclic hydrogen-bonded complexes with two or three water molecules. In the larger clusters, however, water molecules begin to retain the structure of pure water clusters and segregate from SO2. Infrared absorption assignments for the small clusters are discussed to resolve a possible incorrect assignment in a recent spectroscopic experiment on the clusters.展开更多
Based on the boron-containing thermally activated delayed fuorescence(TADF)compound p-AC(AC:acridine)5,9-dioxa-13 b-boranaphtho[3,2,1-de]anthracene(a),a series of new TADF molecules b1-b4 were designed via adding two ...Based on the boron-containing thermally activated delayed fuorescence(TADF)compound p-AC(AC:acridine)5,9-dioxa-13 b-boranaphtho[3,2,1-de]anthracene(a),a series of new TADF molecules b1-b4 were designed via adding two nitrogen atoms at the AC donor part.Density functional theory and time-dependent density functional theory calculations were performed on the frontier orbital energy levels,emission spectra,singlet-triplet states energy gaps(?EST),reverse intersystem crossing(RISC)rate constant(kRISC)for compounds a and b1-b4.Our calculation results show that the maximum emission wavelengths of b1-b4 are significantly blue-shifted by47-125 nm compared with that of a.Molecules b1 and b3 exhibit dark-blue emission,while molecules b2 and b4 display light-blue emission,indicating that these four derivatives could be potential organic light-emitting diode(OLED)candidates with blue-light emitting.Moreover,we found the RISC processes in a,b2,and b4 can occur not only from T_(1) state to S_(1) state,but also from T_(2) state to S_(1) state significantly,while the RISC processes in b1 and b3 mainly take place via the T_(2)→S_(1) hot exciton way.Importantly,the T_(1)→S_(1) kRISC values of b2 and b4 are predicted to be two to three times of that of a,indicating enhanced TADF property.Our results not only provide two promising boron-based TADF candidates(b2 and b4),but also offer useful theoretical basis for the design of blue OLED materials.展开更多
Density functional theory B3LYP/6-311 G＊ method was used in the geometry optimization and frequency calculation on Si5X （X = Li, Be, B, C, N, O, E Na, Mg, Al, Si, P, S, Cl） clusters. The influence of the doped seco...Density functional theory B3LYP/6-311 G＊ method was used in the geometry optimization and frequency calculation on Si5X （X = Li, Be, B, C, N, O, E Na, Mg, Al, Si, P, S, Cl） clusters. The influence of the doped second and third period element impurities on the structure and stability of Si5X clusters with C2p symmetry has been investigated, and the thermal stability and dynamic activity have also been discussed.展开更多
The configuration of[PdCl_2(C_2H_4OH)]^- has been studied by pseudopotential ab initio method.A cis isomer was found to be the reaction intermediate in the Wacker process.
The density functional theory B3LYP/6-311g* method is used in the geometry optimization and frequency calculation on Si4X (X = Li, Be, B, C, N, O, F) clusters. The equi- librium structures of these clusters are quas...The density functional theory B3LYP/6-311g* method is used in the geometry optimization and frequency calculation on Si4X (X = Li, Be, B, C, N, O, F) clusters. The equi- librium structures of these clusters are quasi-trigonal bipyramidal structures with C2v symmetry. The periodicity of their thermal stabilities and vibration spectra has been discussed. The influence of the inserted second period element impurities for the structures and stabilities of the Si5 clusters have also been investigated.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.21103003）.
文摘The lowest energy structures of peroxynitric acid have been studied with B3LYP/6-311＋ G（2d,2p） method. The potential energy surfaces （PES） along the O-N and O-O bonds have been scanned at CCSD（T）/aug-cc-pVDZ level, respectively. The calculated results show that on the O-N PES, the O3-N4 bond length of the loose transition state is 2.82A^° and the corresponding energy barrier is 25.6 kcal/mol, while on the O-O PES, the loose transition state with of O2-O3 bond length of 2.35A^° has the energy barrier of 37.4 kcal/mol. Thus the primary reaction path for peroxynitric acid is the dissociation into HO2 and NO2.
基金This work was supported by the National Natural Science Foundation of China （No.20903101 and No.21103003）.
文摘Using density functional theory and polarizable continuum models, we study the Raman spectra of aqueous peroxynitric acid. The calculated results indicate that the solvent effect has significant influence on the electric dipole transition moments between the ground and excited electronic state and Raman polarizabilities. The theoretical Raman spectra agree well with the experimental results. From the experimental depolarization ratio, we can conclude that peroxynitric acid is not a plane molecule. We also find that the hydrogen bond can enhance IR intensity of hydroxyl group by several times.
文摘This article described the characteristics of the liquid nitrogen engine's ideal open cycle.Using two interconnecting strokes to achieve the power output can mitigate the trade-off between high efficiency and the potential mechanical complexity of multiple-cylinder engines. The total specific energy of the binary media (methane-nitrogen) cycle system could be much higher than the unitary medium (liquid nitrogen) cycle system. By theoretical analysis, the reasonably acceptable driving range proved the feasibility of the liquid nitrogen engine used for supplying power for a lightweight car.
基金the National Natural Science Foundation of China (No. 29802006) the Teaching and Research Award Program for Outstanding Young Teachers in Higher Education Institutions of MOE P.R.C. and Tsinghua University.
文摘The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving a-COOH or b-COOH group had energy barriers of DE = 58.67 kJmol-1 and 103.94 kJmol-1, respectively. These results were in agreement with the experimental data. So the a-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not b-COOH group.
基金supported by the Foundation of Education Committee of Liaoning Province (990321076)
文摘The reaction mechanism of PCl3/H2 on silicon substrate surface （simulated by Si4 cluster） was investigated with Density Functional Theory （DFT） at the B3LYP/6-311G^＊＊ level. On silicon substrate, PCl3 firstly undergoes dissociative adsorption, and then the adsorption product reacts with H2 via a four-step multi-channel mode to give the final product PSi4 cluster. The geometries at each stationary point were fully optimized. The possible transition states were determined by vibrational mode analysis and IRC verification. And finally, the main reaction channel was given.
基金supported by the Natural Scientific Research and Overall innovation plan major project of Shaanxi Provincial Education Office of China(No.2012KTCL03-16)the National Natural Science Foundation of China(No.21373178)+2 种基金the Natural Scientific Research Foundation of Shaanxi Provincial Education Office(No.2013Jk0668)the National College Students'innovation and entrepreneurship training program(201310719002)the special fund of Yan’an University(No.YDZ2013-10)
文摘Two Pb^Ⅱ coordination polymers [Pb（oba）（2,2′-bipy）]·1.5H2O（1） and [Pb（oba）（phen）]（2）（H2oba = 2,4-oxybis（benzoic acid）, 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline） were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. Structures of compounds 1 and 2 are similar. Compounds 1 and 2 show 1D wavy chains, which are further connected through aromatic π-π stacking interactions to expand into 2D wavelike networks. The crystal structure of 2,4-oxybis（benzoic acid） ligand（3） was obtained, and its full geometry optimization was carried out by using DFT methods at the B3LYP/6-31G（d） level. The calculated data show that the bond distances and bond angles were very close to the experimental data. The values of the frontier orbital energies indicate that this configuration is stable. Moreover, the solid-state fluorescence properties of 1-3 have also been investigated.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11564019,11574114,11147158,91221301 and 11264020the Natural Science Foundation of Jilin Province under Grant No 20150101003JC
文摘An accurate theoretical study on the MgH radical is reported by adopting the high-level relativistic MRCI＋Q method with a quintuple-zeta quality basis set. The reliable potential energy curves of the five A-S states of MgH are derived. Then the associated spectroscopic parameters are determined and found to be in good accordance with the available experimental results. The permanent dipole moments （PDMs） and the spin-orbit （SO） matrix elements of A-S states are computed. The results show that the abrupt changes of PDMs and SO matrix elements are attributed to the variations of electronic configurations at the avoided crossing point. The SOC effect leads to the five A-S states split into ten Ω states and results in the double potential well of （2）1//2 state. Finally, the transition properties from the （2）1//2, （1）3//2 and （3）1//2 states to the ground state X2∑＋1//2 transitions are obtained, including the transition dipole moments, Franck-Condon factors and radiative lifetimes.
基金Supported by the Fundamental Research Funds for the Central Universitiesthe Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe National Natural Science Foundation of China under Grant No 11204123
文摘The carrier mobility of two-dimensional tetragonal carbon allotrope （T-CA） from porous graphene is investigated by first-principles calculations. T-CA can be constructed from divacancy and Stone-Thrower--Wales defects from graphene. T-CA is a direct semiconductor with a band gap of 0.4 eV at F point. T-CA possesses a high carrier mobility of the order of 104 cm2V-ls-1. As our study demonstrates, T-CA has potential applications for next-generation electronic materials.
文摘The mechanism and kinetics for the decomposition of 3-hydroxy-3-methyl-2-butanone have been studied by using the ab initio RHF/3-21G method. The calculated activation barrier of the reaction is 249.6kJ/mol which is in reasonable agreement with the experimental data (222.2±3kJ/mol). The calculated results show that the decomposition is a concerted process with hydrogen transferring and bond breaking via a five-membered cyclic transition state. The thermal rate constants of the decomposition are obtained by calculating microcanonical probability fluxes through transition state1.
基金This work was supported by the National Natural Science Foundation of China (No. 20303010), NKStar HPC Program and the Science Foundation of Nankai University
文摘The reaction mechanism between CC12 and armchair single-walled carbon nanotubes （ASWCNTs） （3,3） and （4,4） has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CC12 adding to ASWCNT （3,3） and （4,4） are computed and compared. The lower barrier of CC12 forms cycloaddition isomer on （3,3） maybe because the strain energy of （3,3） is larger than that of （4,4）. Our theoretical results are consistent with the experimental results.
基金Supported by the General Program of the Applied Basic Research of Science and Technology Department of Yunnan Province (No.2008ZC095)the Scientific Research Fund of Yunnan Provincial Education Department (No.08Y0195)supported by the Key Laboratory of Forest Resources Conservation and Use in the Southwest Mountains of China (Southwest Forestry University)
文摘The reaction of Au＋（1S,3D） with CS2 has been investigated at the B3LYP and CCSD（T） levels of theory.The identified reaction pathways revealed that the experimentally observed products,AuS＋ and AuCS＋,can be produced by the insertion of Au＋ into C-S bond.The calculated energetics shows that the reactions on singlet surface lead to excited-state products,AuS＋（1Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 1S,and have notable energy barriers,whereas the reactions on triplet surface producing the ground state products of AuS＋（3Σ） ＋ 1CS and AuCS＋（1Σ） ＋ 3S are energetically much more favorable.This result suggests that the minor formations of AuS＋ and AuCS＋ observed in the previous experiment under room-temperature condition should result from the reactions of excited-state Au＋（3D） with CS2.Further,the possibility for singlet-triplet surface crossing was also discussed by approximately determining the crossing region.
文摘Semi-empirical method PM3 was used to study the geometry and vibrational spectrum of N-(2-hydroxy-l-naphthyl-methylene)-l-pyrenamine (NPY) with the intermediate hydrogen bond. Results are comparable to experimentations. Based on results of both NPY and its model, N-(2-hydroxy-l-naphthyl-methylene)aniline, it was found that the N-(2-hydroxy-l-naphthyl-methylene) group is principally responsible for the special hydrogen bonding through conjugation effect.
文摘We compute the thermodynamic and the kinetic properties for the reaction: HCOCN→HCH+CO using the statistical theory and the transition-state theory.The equi- librium constants and the rate coefficients of this reaction are also reported here,and the half lives of formyl cyanide at different temperatures are first estimated in this work.
文摘The geometries and vibrational frequencies of the ground and low-lying excited states for B_3, B_3^- and B_3^+ are determined with the energy gradient method using the polarized double-zeta(6-31G*) basis set. The stabilities for the states of B_3,B_3^- and B_3^+ have been investigated based on the vibrational analysis. The correlation energy obtained for each state is considered with the configuration interaction (CISD+Q) technique. B_3 and B_3^+ have stable equilateral triangle geometry, while B_3^- has stable equilateral triangle, isosceles triangle and linear geometries. The Jahn-Teller distortion for a ~3E' state of B_3^- in D_(3h) symmetry is also discussed.
基金Sponsored by the National Natural Science Foundation of China (No. 50473062, 50673069)Key Project of Natural Science of Sichuan Provincial Education Department (No. 07ZA093 )Scientific Research and Innovation Team Fund of Sichuan Normal University (No. 025156)
文摘Molecular structures, reorganization energies and charge transport matrix elements of coronene and its fluoro-, hydroxyl- and sulfhydryl-substituted derivatives have been studied at the B3LYP/6-31G＊＊ level. Based on the semi-classical model of electron transfer, charge transport rate constants of the title molecules have been calculated. The results indicate that the coronene molecule is helpful to the transport of negative charge, and the transport rate of positive charge is between those of hexaazatriphenylene and triphenylene.
基金supported by the National Natural Science Foundation of China (20528706)the China Postdoctoral Science Foundation (20090450385)
文摘The intermolecular clusters of sulfur dioxide with water, SO2（H2O）n （n = 2～5）, are studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets （6-311＋＋G（d,p） and aug-cc-pVDZ）. The equilibrium geometries, intermolecular binding energies, and anharmonic frequencies of the clusters are calculated and compared with those of pure water clusters and available experiments. SO2 tends to form cyclic hydrogen-bonded complexes with two or three water molecules. In the larger clusters, however, water molecules begin to retain the structure of pure water clusters and segregate from SO2. Infrared absorption assignments for the small clusters are discussed to resolve a possible incorrect assignment in a recent spectroscopic experiment on the clusters.
基金supported by the National Natural Science Foundation of China(No.22173008)。
文摘Based on the boron-containing thermally activated delayed fuorescence(TADF)compound p-AC(AC:acridine)5,9-dioxa-13 b-boranaphtho[3,2,1-de]anthracene(a),a series of new TADF molecules b1-b4 were designed via adding two nitrogen atoms at the AC donor part.Density functional theory and time-dependent density functional theory calculations were performed on the frontier orbital energy levels,emission spectra,singlet-triplet states energy gaps(?EST),reverse intersystem crossing(RISC)rate constant(kRISC)for compounds a and b1-b4.Our calculation results show that the maximum emission wavelengths of b1-b4 are significantly blue-shifted by47-125 nm compared with that of a.Molecules b1 and b3 exhibit dark-blue emission,while molecules b2 and b4 display light-blue emission,indicating that these four derivatives could be potential organic light-emitting diode(OLED)candidates with blue-light emitting.Moreover,we found the RISC processes in a,b2,and b4 can occur not only from T_(1) state to S_(1) state,but also from T_(2) state to S_(1) state significantly,while the RISC processes in b1 and b3 mainly take place via the T_(2)→S_(1) hot exciton way.Importantly,the T_(1)→S_(1) kRISC values of b2 and b4 are predicted to be two to three times of that of a,indicating enhanced TADF property.Our results not only provide two promising boron-based TADF candidates(b2 and b4),but also offer useful theoretical basis for the design of blue OLED materials.
基金This work was supported by Foundation of Education Committee of Liaoning Province (No. 990321076)
文摘Density functional theory B3LYP/6-311 G＊ method was used in the geometry optimization and frequency calculation on Si5X （X = Li, Be, B, C, N, O, E Na, Mg, Al, Si, P, S, Cl） clusters. The influence of the doped second and third period element impurities on the structure and stability of Si5X clusters with C2p symmetry has been investigated, and the thermal stability and dynamic activity have also been discussed.
文摘The configuration of[PdCl_2(C_2H_4OH)]^- has been studied by pseudopotential ab initio method.A cis isomer was found to be the reaction intermediate in the Wacker process.
基金This work was supported by the Foundation of Education Committee of Liaoning Province (990321076)
文摘The density functional theory B3LYP/6-311g* method is used in the geometry optimization and frequency calculation on Si4X (X = Li, Be, B, C, N, O, F) clusters. The equi- librium structures of these clusters are quasi-trigonal bipyramidal structures with C2v symmetry. The periodicity of their thermal stabilities and vibration spectra has been discussed. The influence of the inserted second period element impurities for the structures and stabilities of the Si5 clusters have also been investigated.
