1.

Synthesis,Crystal Structure and Spectroscopic Properties of 1,2Benzothiazine Derivatives:An Experimental and DFT Study





MUHAMMAD Nadeem Arshad TARIQ Mahmood ATHER Faroque Khan MUHAMMAD ZiaUrRehman ABDULLAH M.Asiri ISLAM Ullah Khan RIFFATUnNisa KHURSHID Ayub AZAM Mukhtar MUHAMMAD Tariq Saeed《结构化学》,2015年第34卷第1期


1,2Benzothiazine derivatives methyl 3methoxy4oxo3,4dihydro2Hbenzo[e] [1,2]thiazine3carboxylate 1,1dioxide(1) and methyl 2ethyl3hydroxy4oxo3,4dihydro2Hbenzo[e][1,2]thiazine3carboxylate 1,1dioxide(2) were synthesized, and characterized by spectroscopic techniques; 1HNMR 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 singlecrystal Xray diffraction analysis. Geometric properties were calculated by the B3 LYP method of density functional theory(DFT) at the 631G+(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 p1.2a.u. between the experiment and the theory. The discrepancy between experimental and theoretical data in the lowmomentum region is explained with the distorted wave effect.

3.

Experimental and Theoretical Investigation of Valence Orbitals in 1,4Dioxane 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, 4dioxane 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 HartreeFock method and density functional theory with 6311＋＋G^＊＊ and AUGCCPVTZ 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 HartreeFock and density functional theory(DFT) calculations employing 631G,6311 G^** and AUGccpVQZ basis sets.For the summed momentum distribution of 8α′ 5α″ 7α′ orbitals,the DFT/.AUGccpVQZ calculation gives the best fit.A very large and diffuse basis set,AUGccpVQZ,is employed in the calculations to approach the HartreeFock limit of the basis set,but the improvement of the calculation quality is little in comparison with that calculated with the 6311 G^** basis set,This indicates that the 6311 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 CCOOH 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(CBSQ) 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 CBSQ 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 CCOOH 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 1,8Naphthalimide 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 4phenoxy1,8naphthalimide derivatives, namely 4phenoxyN（2hydroxyethyl）1,8naphthalimide（1）,4（2tertbutylphenoxy）N（2hydroxyethyl）1,8naphthalimide（2）, and 4[2,4di（tertbutyl）]phenoxyN（2hydroxyethyl）1,8naphthalimide（3）, are investigated by density functional theory（DFT） and timedependent density functional theory（TDDFT） 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/6311＋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/6311＋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 tertbutyl substituents onto the phenoxy groups, suggesting redshift 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 NF_{3}





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 highresolution electron momentum spectroscopy with the highlevel calculations. The experimental binding energy spectra and the momentum distributions of each orbital were compared with the results of HartreeFock, density functional theory （DFT）, and symmetryadapted cluster configurationinteraction （SACCI） methods. SACCI and DFTB3LYP with the augccpVTZ 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 DFTB3LYP are even better than those using the highlevel SACCI 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·mol1. 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 (ELUMOFeEHOMOCys and ELUMOCysEHOMOFe) 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 6311++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 ChenSheng LI Jun LIU ChunWanFujian 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 allelectron or effective core potential ab initio method at the selfconsistent field level using basis sets with diffuse and polarization functions. The boronboron and boronhalide (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 threecentered twoelectron (3c2e) BBB bonds localized on each of the faces of the B4 tetrahedron are derived for B4X4 clusters. The HOMOLUMO 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 Fdoped 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 firstprinciples calculations based on the hybrid densityfunctional theory at the B3LYP/6311G level. The geometries are found to undergo a structural change from twodimensional to threedimensional structure when the cluster size n equals 3. On the basis of the obtained lowestenergy geometries, the size dependencies of cluster properties, such as averaged binding energy, fragmentation energy, secondorder 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 1cyclopentylpiperazine: 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


FTIR and Raman spectra of 1cyclopentylpiperazine(1cppp)have been experimentally examined in the region of 4000–200cm1.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 631++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(equatorialaxial)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 631 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 singleelectron halogen bond complexes H_3C…BrY(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 singleelectron halogen bond complexes H3C…BrY(Y = H,CCH,CN,NC,C2H3) have been investigated by theoretical calculation methods.The geometries were optimized and frequencies calculated at the B3LYP/6311++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 MP2/6311++G level.For each H3C…BrY complex,a singleelectron 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 DFTB3LYP and MP2 methods at the 6311++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 lonepair electrons to the σ(OH)* or σ(OH)* 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 spinorbit 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= 16）





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 C_{n}H_{2n+2} （n=16） are studied by B3LYP/TZVP based on the most stable geometries using the B3LYP/augccpVTZ method.Vertical ionization energies are produced using the SAOP/etpVQZ model for the complete valence space.The highest occupied molecular orbital （HOMO） investigations indicate the pelectron profiles in methane,ethane,propane,and nbutane.By increasing the number of carboncarbon bonds in lower momentum regions,the s,phybridized 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 carboncarbon 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 isomerdependent 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 secondorder 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 closepacked 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 3,6Linked Carbazole Trimers by Timedependent 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 3,6linked carbazole trimers, two conjugated oligomers with different linkages of carbazole, were studied by the density functional theory with BeckeLeeYoungParr composite exchange correlation functional (B3LYP). The absorption spectra of these compounds were also investigated by timedependent density functional theory (TDDFT) with 631G* basis set. The calculated results indicated that the HOMO and LUMO of the 2,7 and 3,6linked carbazole trimers are both slightly destabilized on going from methyl substitution to secbutyl substitution. Both IP and EA exhibit their good holetransporting but poor electron accepting ability. The presence of alkyl groups on the nitrogen atoms does not affect the intrachain 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 HartreeFock （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.
