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1.  Synthesis,Crystal Structure and Spectroscopic Properties of 1,2-Benzothiazine Derivatives:An Experimental and DFT Study  
   MUHAMMAD Nadeem Arshad  TARIQ Mahmood  ATHER Faroque Khan  MUHAMMAD Zia-Ur-Rehman  ABDULLAH M.Asiri  ISLAM Ullah Khan  RIFFAT-Un-Nisa  KHURSHID Ayub  AZAM Mukhtar  MUHAMMAD Tariq Saeed《结构化学》,2015年第34卷第1期
   1,2-Benzothiazine derivatives methyl 3-methoxy-4-oxo-3,4-dihydro-2H-benzo[e] [1,2]thiazine-3-carboxylate 1,1-dioxide(1) and methyl 2-ethyl-3-hydroxy-4-oxo-3,4-dihydro-2Hbenzo[e][1,2]thiazine-3-carboxylate 1,1-dioxide(2) were synthesized, and characterized by spectroscopic techniques; 1H-NMR and infrared(IR) spectroscopy. Crystals of 1 and 2 were grown by slow evaporation of methanol and ethyl acetate, respectively and their crystal structures were investigated by single-crystal X-ray diffraction analysis. Geometric properties were calculated by the B3 LYP method of density functional theory(DFT) at the 6-31G+(d) basis set to compare with the experimental data. Simulated properties were found in strong agreement with the experimental ones. Intermolecular forces have also been modeled in order to investigate the strength of packing and strong hydrogen bonding was observed in both compounds 1 and 2. Electronic properties such as Ionization Potential(IP), Electron Affinities(EA) and coefficients of the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of com- pounds 1 and 2 were simulated for the first time.    

2.  Highest Occupied Molecular Orbital of Cyclopentanone by Binary (e, 2e) Spectroscopy  
   张书锋 宁传刚 邓景康 任雪光 苏国林 杨铁成 黄艳茹《中国物理快报》,2006年第23卷第3期
   We report the first measurements of the momentum profiles of highest occupied molecular orbital (HOMO) and the complete valence shell binding energy spectra of cyclopentanone with impact energies of 600 and 1200 eV by a binary (e, 2e) spectrometer. The experimental momentum profiles of the HOMO orbital are compared with the theoretical momentum distribution calculated using the Hartree Fock and density functional theory methods with various basis sets. However, none of these calculations gives a completely satisfactory description of the momentum distributions of the HOMO 762. The inadequacy of the calculations could result in the intensity difference of the second maximum at p-1.2a.u. between the experiment and the theory. The discrepancy between experimental and theoretical data in the low-momentum region is explained with the distorted wave effect.    

3.  Experimental and Theoretical Investigation of Valence Orbitals in 1,4-Dioxane by Electron momentum Spectroscopy  
   杨铁成 宁传刚 苏国林 邓景康 张书锋 任雪光 黄艳茹《中国物理快报》,2006年第23卷第5期
   The binding energy spectrum of all valence orbitals and the momentum distributions of highest occupied molecular orbital (HOMO: 8ag), 7bu+7ag, 4bu, 2bg +4ag and 2au in 1, 4-dioxane are investigated by electron momentum spectroscopy (EMS) with 600 eV impact energy. The experimental results are consistent with theoretical calcula- tions of C2h chair conformation using the Hartree-Fock method and density functional theory with 6-311++G^** and AUG-CC-PVTZ basis sets.    

4.  Electron Momentum Spectroscopy of the Frontier Orbitals of Chlorodifluoromethane  
   徐春凯 陈向军 等《中国物理快报》,2002年第19卷第12期
   We report on the first measurement of the electron momentum distributions of the three outermost valence orbitals for chorodifluoromethane(CHF2Cl)by binary(e,2e) electron momentum spectroscopy.The experimental data are compared with Hartree-Fock and density functional theory(DFT) calculations employing 6-31G,6-311 G^** and AUG-cc-pVQZ basis sets.For the summed momentum distribution of 8α′ 5α″ 7α′ orbitals,the DFT/.AUG-cc-pVQZ calculation gives the best fit.A very large and diffuse basis set,AUG-cc-pVQZ,is employed in the calculations to approach the Hartree-Fock limit of the basis set,but the improvement of the calculation quality is little in comparison with that calculated with the 6-311 G^** basis set,This indicates that the 6-311 G^** basis set is nearly saturated for the calculations of these three orbitals of CHF2Cl,and it is unnecessary to employ a larger basis set in the calculations.    

5.  Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids  
   曾晖  赵俊  肖循《中国物理 B》,2013年第22卷第2期
   Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies(BDEs) for 15 acids.These compounds are studied by utilizing the hybrid density functional theory(DFT)(B3LYP,B3PW91,B3P86,PBE1PBE) and the complete basis set(CBS-Q) method in conjunction with the 6311G** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.    

6.  Theoretical Study on the Electronic Structures and Spectral Properties of 1,8-Naphthalimide Derivatives  
   王艳  高慧  杨平  聂光华  宋新建《结构化学》,2014年第33卷第6期
   The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-(2-hydroxyethyl)-1,8-naphthalimide(1),4-(2-tert-butylphenoxy)-N-(2-hydroxyethyl)-1,8-naphthalimide(2), and 4-[2,4-di(tert-butyl)]phenoxy-N-(2-hydroxyethyl)-1,8-naphthalimide(3), are investigated by density functional theory(DFT) and time-dependent density functional theory(TD-DFT) calculations in conjunction with polarizable continuum models(PCMs). Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311+G(d,p) method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311+G(d,p) level. We find that the gap between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.    

7.  Electron momentum spectroscopy of NF3  
   李嘉明  苗雨润  邓景康  宁传刚《中国物理 B》,2014年第11期
   The electronic structure of nitrogen trifluoride was investigated by combining the high-resolution electron momentum spectroscopy with the high-level calculations. The experimental binding energy spectra and the momentum distributions of each orbital were compared with the results of Hartree-Fock, density functional theory (DFT), and symmetry-adapted- cluster configuration-interaction (SAC-CI) methods. SAC-CI and DFT-B3LYP with the aug-cc-pVTZ basis set can well reproduce the binding energy spectra and the observed momentum distributions of the valence orbitals except 1 a2 and 4e orbitals. It was found that the calculated momentum distributions using DFT-B3LYP are even better than those using the high-level SAC-CI method.    

8.  半胱氨酸在碳钢与硫酸界面的缓蚀行为  被引次数:2
   OZCAN Muzaffer KARADAGG Faruk DEHRII Ilyas《物理化学学报》,2008年第24卷第8期
   Interfacial behavior of cysteine (Cys) between mild steel and sulfuric acid solution as a corrosion inhibitor has been studied with electrochemical AC (alternating current) and DC (direct current) techniques at (25.0±0.1) ℃. The AC impedance results were evaluated using equivalent circuits in which a constant phase element (CPE) has been replaced with double layer capacitance (Cdl) to represent the frequency distribution of experimental data. Changes in impedance parameters (charge transfer resistance and double layer capacitance) indicated that cysteine molecules acted by accumulating at the metal/solution interface. The fractional coverage of the metal surface (θ) was determined using AC impedance results and it was found that the adsorption of cysteine on the mild steel surface followed a Langmuir isothermmodel with a standard free energy of adsorption (⊿G0ads) of -35.1 kJ·mol-1.  To clarify the type of interaction between mild steel surface and cysteine molecules with a molecular orbital approach, electronic properties, such as, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy, and the frontier molecular orbital coefficients have been calculated. Energy gaps for the interaction of mild steel surface and cysteine molecules (ELUMOFe-EHOMOCys and ELUMOCys-EHOMOFe) were used to determine whether cysteine molecules acted as electron donors or electron acceptors when they interacted with the mild steel surface. The local reactivity was evaluated through the condensed Fukui indices. Theoretical calculations were carried out using the density functional theory (DFT) at B3LYP level with the 6-311++G(d,p) basis set for all atoms by Gaussian 03W program.    

9.  Theoretical study on tetranuclear boron clusters: B4X4 (X = H, F, Cl, Br, I)  
   LIN  Chen-Sheng LI  Jun LIU  Chun-WanFujian Institute of Research on the Structure of Matter  Chinese Academy of Sciences  State Key Laboratory of Structural Chemistry  Fuzhou  Fujian 350002  China《中国化学》,1994年第4期
   The molecular orbitals for B4H4, B4F4, B4Cl4, B4Br4 and B4I4 have been calculated by using all-electron or effective core potential ab initio method at the self-consistent field level using basis sets with diffuse and polarization functions. The boron-boron and boron-halide (-hydrogen) distances of these cage compounds are optimized with three kinds of basis sets constrained to a tetrahedral symmetry. According to the localization scheme of Boys, four three-centered two-electron (3c2e) B-B-B bonds localized on each of the faces of the B4 tetrahedron are derived for B4X4 clusters. The HOMO-LUMO energy gaps, atomization energies and Mulliken overlap populations of these compounds indicate that the stabilities of the clusters decrease in the sequence of B4F4 > B4Cl4, B4H4 > B4Br4 > B4I4.    

10.  Assessment of delocalized and localized molecular orbitals through electron momentum spectroscopy  
   刘源  张凌峰  宁传刚《中国物理 B》,2014年第6期
   Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow's work titled "Is it time to retire the hybrid atomic orbital?" [J. Chem. Educ. 88, 860 (2011)]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental (e, 2e) results.    

11.  Structures,stabilities, and electronic properties of F-doped Sin (n=1~12) clusters:Density functional theory investigation  
   张帅  蒋华龙  王萍  卢成  李根全  张萍《中国物理 B》,2013年第12期
   The geometries, stabilities, and electronic properties of FSin (n=1~12) clusters are systematically investigated by using first-principles calculations based on the hybrid density-functional theory at the B3LYP/6-311G level. The geometries are found to undergo a structural change from two-dimensional to three-dimensional structure when the cluster size n equals 3. On the basis of the obtained lowest-energy geometries, the size dependencies of cluster properties, such as averaged binding energy, fragmentation energy, second-order energy difference, HOMO–LUMO (highest occupied molecular orbital–lowest unoccupied molecular orbital) gap and chemical hardness, are discussed. In addition, natural population analysis indicates that the F atom in the most stable FSin cluster is recorded as being negative and the charges always transfer from Si atoms to the F atom in the FSin clusters.    

12.  Vibrational investigation of 1-cyclopentylpiperazine: A combined experimental and theoretical study  
   BAGLAYAN zge  KESAN Gürkan  PARLAK Cemal  ALVER zgür  SENYEL Mustafa《中国科学:物理学 力学 天文学(英文版)》,2014年第57卷第9期
   FT-IR and Raman spectra of 1-cyclopentylpiperazine(1cppp)have been experimentally examined in the region of 4000–200cm-1.The optimized geometric parameters,conformational equilibria,normal mode frequencies and corresponding vibrational assignments of 1cppp(C9H18N2)are theoretically examined by means of B3LYP hybrid density functional theory(DFT)method together with 6-31++G(d,p)basis set.On the basis of potential energy distribution(PED)reliable vibrational assignments have been made and the thermodynamics functions,highest occupied and lowest unoccupied molecular orbitals(HOMO and LUMO)of 1cppp have been predicted.Calculations are employed for four different conformations in C1 and Cs point groups of 1cppp in gas phase.Comparison between the experimental and theoretical results indicates that B3LYP method is able to provide satisfactory results for predicting vibrational frequencies and the structural parameters,vibrational frequencies and assignments.Furthermore,C1(equatorial-axial)point group has been found as the most stable conformer of 1cppp.    

13.  The geometry structures and electronic properties of Li_mB_n(m+n=12) clusters  
   阮文  谢安东  伍冬兰  罗文浪  余晓光《中国物理 B》,2014年第3期
   The geometric structures, electronic properties, total and binding energies, harmonic frequencies, the highest occupied molecular orbital to the lowest unoccupied molecular orbital energy gaps, and the vertical ionization potential energies of small LimBn (m+ n = 12) clusters were investigated by the density functional theory B3LYP with a 6-31 I+G (2d, 2p) basis set. All the calculations were performed using the Gaussian09 program. For the study of the LimBn clusters, the global minimum of the B 12 cluster was chosen as the starting point and the boron atoms were gradually replaced by Li atoms. The results showed that as the number of Li atoms increased, the stability of the LimBn cluster decreased and the physical and chemical properties became more active. In addition, on average there was a large charge transfer from the Li atoms to the B atoms.    

14.  Theoretical study of the interaction mechanism of single-electron halogen bond complexes H_3C…Br-Y(Y=H,CN,NC,CCH,C_2H_3)  
   LI ZhiFeng  SHI XiaoNing  TANG HuiAn & ZHANG JunYan College of Life Science    Chemistry  Tianshui Normal University  Tianshui   China  Lanzhou Institute of Chemical Physics  Chinese Academy of Sciences  Lanzhou《中国科学:化学》,2010年第1期
   The characteristics and structures of single-electron halogen bond complexes H3C…Br-Y(Y = H,CCH,CN,NC,C2H3) have been investigated by theoretical calculation methods.The geometries were optimized and frequencies calculated at the B3LYP/6-311++G level.The interaction energies were corrected for basis set superposition error(BSSE) and the wavefunctions obtained by the natural bond orbital(NBO) and atom in molecule(AIM) analyses at the MP2/6-311++G level.For each H3C…Br-Y complex,a single-electron Br bond is f...    

15.  Theory Studies on the Intermolecular Interactions of Urea Nitrate with RDX  
   杜拴丽  张文艳  曹端林  侯素青  任福德《结构化学》,2011年第30卷第5期
   Six fully optimized geometries of urea nitrate cation and RDX complexes have been obtained with DFT-B3LYP and MP2 methods at the 6-311++G** level. The intermolecular interaction energies have been calculated with basis set superposition error (BSSE) and zero point energy (ZPE) correction. The nature of intermolecular interaction has been revealed by the analysis of AIM and NBO. The results indicate that the greatest binding energy of urea nitrate with RDX is –82.47kJ/mol. The O–H…O and N–H…O hydrogen bonds are important intermolecular interactions of urea nitrate cation with RDX, and the origin of hydrogen bonds is the oxygen atom offering its lone-pair electrons to the σ(O-H)* or σ(O-H)* antibonding orbital. The intermolecular interactions strengthen the N–NO2 bond, leading to the reduced sensitivity of urea nitrate and RDX mixture explosive.    

16.  Interpretation of the Experimental Electron Momentum Spectra of 5e1/2 and 5e3/2 Orbitals of CF3I with Relativistic Calculations  
   刘昆  宁传刚  邓景康《中国物理快报》,2010年第27卷第7期
   With our newly developed method, we calculate the spin-orbit splitting states 5e1/2 and 5e3/2 of the CF3I molecule incorporating the relativistic effects. Our theoretical results agree excellently with the recent experimental observations. The present study shows that relativistic effects can evidently change the electron momentum distributions of molecular orbitals when a medium Z element is included, such as iodine.    

17.  Orbital responses to methyl sites in CnH2n+2 (n= 1-6)  
   杨则金  程新路  朱正和  杨向东《中国物理 B》,2012年第2期
   Orbital responses to methyl sites in CnH2n+2 (n=1-6) are studied by B3LYP/TZVP based on the most stable geometries using the B3LYP/aug-cc-pVTZ method.Vertical ionization energies are produced using the SAOP/et-pVQZ model for the complete valence space.The highest occupied molecular orbital (HOMO) investigations indicate the pelectron profiles in methane,ethane,propane,and n-butane.By increasing the number of carbon-carbon bonds in lower momentum regions,the s,p-hybridized orbitals are built and display strong exchange and correlation interactions in lower momentum space (P<0.50 a.u.).Meanwhile,the relative intensities of the isomers in lower momentum space show the strong bonding number dependence of the carbon-carbon bonds,meaning that more electrons have contributed to orbital construction.The study of representative valence orbital momentum distribution further confirms that the structural changes lead to evident electronic rearrangement over the whole valence space.An analysis based on the isomers reveals that the valence orbitals are isomer-dependent and the valence ionization energy experiences an apparent shift in the inner valence space.However,such shifts are greatly reduced in the outer valence space.Meanwhile,the opposite energy shift trend is found in the intermediate valence space.    

18.  Structure and magnetic properties of Osn (n=11~22) clusters  
   张秀荣  张福星  陈晨  袁爱华《中国物理 B》,2013年第12期
   The structure and magnetic properties of Osn (n=11~22) clusters are systematically studied by using density functional theory (DFT). For each size, the average binding energy per atom, the second-order differences of total energies and the highest occupied molecular orbital (HOMO)–the lowest unoccupied molecular orbital (LUMO) gaps are calculated to analyze the stability of the cluster. The structures of Os14 and Os18 clusters are based on a close-packed hexagonal structure, and they have maximum stabilities, so n=14, 18 are the magic numbers. The 5d electrons play a dominant role in the chemical reaction of Osn clusters. The magnetic moments of Osn clusters are quenched around n=12, and when n=18~22 the value approximates to zero, due to the difference of electron transfer.    

19.  Theoretical Study on the Optical Properties for 2,7- and 3,6-Linked Carbazole Trimers by Time-dependent Density Functional Theory  
   王寒露  王学业  王玲  王衡亮  刘爱虹《结构化学》,2007年第26卷第4期
   Electronic properties, such as HOMO and LUMO energies, band gaps, ionization potential (IP) and electron affinity (EA) of 2,7- and 3,6-linked carbazole trimers, two conjugated oligomers with different linkages of carbazole, were studied by the density functional theory with Becke-Lee-Young-Parr composite exchange correlation functional (B3LYP). The absorption spectra of these compounds were also investigated by time-dependent density functional theory (TD-DFT) with 6-31G* basis set. The calculated results indicated that the HOMO and LUMO of the 2,7- and 3,6-linked carbazole trimers are both slightly destabilized on going from methyl substitution to sec-butyl substitution. Both IP and EA exhibit their good hole-transporting but poor electron- accepting ability. The presence of alkyl groups on the nitrogen atoms does not affect the intra-chain electronic delocalization along the molecular frame. Thus no significant effect on the band gap and absorption spectra of compounds has been found.    

20.  Investigation of outer valence orbital of CF2Cl2 by a new type of electron momentum spectrometer  
   宁传刚  任雪光  邓景康  苏国林  张书锋  黄峰  李桂琴《中国物理》,2005年第14卷第12期
   Electronic states of CF2Cl2 (dichlorodifluoromethane, Freon 12) have been studied using a new type of electron momentum spectrometer with a very high efficiency at an impact energy of 1200 eV plus binding energy. The experimental electron momentum profiles are compared with the density functional theory (DFT) and Hartree-Fock (HF) calculations. The relationship between orbital assignments in different coordinate systems is discussed. A new method of difference analysis based on the new type of electron momentum spectrometer is used to clarify the ambiguities regarding the orbital ordering.    

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