甘氨酸与水分子间相互作用的理论研究

在密度泛函(DFT)B3LYP/6_311++G(3d,3p)水平,对中性甘氨酸的最小点结构Ip和H2O分子间可能存在的氢键复合物进行全自由度能量梯度优化,发现了三个氢键极小结构A、C和E,其中结构A为最稳定结构,它是H2O与甘氨酸的羧基(-COOH)形成两个氢键的结构,具有C1对称性.分别采用密度泛函理论(DFT)和MP2方法,在6-311++G(3d,3p)水平,对结构A的结构和结合能进行了比较计算,得到结合能ΔEDFT为-41.88 kJ/mol,ΔEMP2为-40.34 kJ/mol.     

低聚壳聚糖衍生物与BSA的作用研究

研究了具有生物相容性的低聚壳聚糖衍生物与活性药物牛血清白蛋白(BSA)之间的作用。合成了聚合度为20的窄分子量分布低聚壳聚糖 (NLCS₂₀)的3种衍生物：N-马来酰化低聚壳聚糖(MNLCS)、N-羧甲基低聚壳聚糖(CNLCS)和N-琥珀酰化低聚壳聚糖(SNLCS)。通过紫外光谱(UV)、荧光光谱和等温滴定微量热仪(ITC)研究了NLCS₂₀衍生物与BSA之间的相互作用。结果表明,BSA的构象在NLCS₂₀衍生物溶液微环境中没有发生变化,活性也没有受到影响。NLCS₂₀衍生物与BSA的作用过程是放热的且是自发进行的,主要作用力是氢键和疏水作用。说明低聚壳聚糖衍生物能够作为潜在的亲水药物如活性医药蛋白或氨基酸的运输载体。     

胸腺嘧啶-BH3构型与性质的DFT和MP2研究

对胸腺嘧啶 BH3复合物分别用B3LYP/6 31G(d)和MP2/6 31G(d)进行计算,以预测该复合物的构型 及结合能,得到了5种构型,并进行了振动分析和自然键轨道分析.对各构型进行了更大基组(6 311+G(2df)和 aug cc pVDZ)的单点能量计算.结果表明,B原子与O原子直接相连的构型(a)、(b)比较稳定,其结合能为90.4 和88.0kJ/mol(B3LYP/6 31G(d),BSSE校正).N原子向B原子的空轨道提供电子形成构型(c)和(d),只找到 了一种由C原子向B原子提供π电子的构型(e).所有构型中均存在电荷授受,各构型的结合能与电荷转移量有 良好的相关性.复合物的形成,使其红外光谱均有不同程度的红移,红移幅度与复合物的稳定性相关.     

Theoretical Study on Destruction Mechanism of 2,3,7,8-TCDD by O3 and NO3

采用B3LYP/6-31G(d)方法优化获得O₃及NO₃降解2,3,7,8-TCDD反应通道上驻点的几何构型, 得到微观反应进程,并采用MP2/6-311G(d,p)//B3LYP/6-31G(d)方法计算得到相关反应的活化能. 研究表明,O₃和NO₃采用不同的方式对2,3,7,8-TCDD进行降解. O₃通过臭氧加成及碳碳双键断裂使2,3,7,8-TCDD降解,而NO₃通过氯取代反应使得2,3,7,8-TCDD上2,3,7,8取代位置上的氯原子被取代为氧原子,从而达到有效降解的目的. O₃降解2,3,7,8-TCDD的反应能垒显著小于NO₃降解2,3,7,8-TCDD的反应能垒,表明O₃降解2,3,7,8-TCDD的能力显著高于NO₃.     

乙醇-水分子团簇(C2H5OH)nH2O(n=1-4)的稳定结构特性研究

采用密度泛函理论M06-2X方法, 在6-311 ++G(2d,2p)// 6-311 ++G(d,p)基组水平上对乙醇-水分子团簇(C2H5OH)nH2O(n=1-4)进行计算, 得到乙醇-水分子团簇的各种稳定构型, 并对乙醇水分子团簇的结构特点进行了分析, 优化的各种低能结构、结构参数、氢键、结合能、平均氢键参数、NBO电荷分布等．结果表明: 最低能稳定结构都是环状的, 而且这些团簇除了形成O―H…O型主氢键外, 还有另一种作用方式C―H…O, 称之为次氢键．虽然C―H…O氢键远弱于O―H…O氢键, 但是对团簇的某些性质也有一定的影响.     

乙醇-水分子团簇(C2H5OH)nH2O(n=1-4)的稳定结构特性研究

采用密度泛函理论M06-2X方法, 在6-311 ++G(2d,2p)// 6-311 ++G(d,p)基组水平上对乙醇-水分子团簇(C2H5OH)nH2O(n=1-4)进行计算, 得到乙醇-水分子团簇的各种稳定构型, 并对乙醇水分子团簇的结构特点进行了分析, 优化的各种低能结构、结构参数、氢键、结合能、平均氢键参数、NBO电荷分布等．结果表明: 最低能稳定结构都是环状的, 而且这些团簇除了形成O―H…O型主氢键外, 还有另一种作用方式C―H…O, 称之为次氢键．虽然C―H…O氢键远弱于O―H…O氢键, 但是对团簇的某些性质也有一定的影响.     

甲醛与乙腈相互作用的理论研究

在HF/ 6 311G(d ,p)、MP2 / 6 311G(d ,p)和B3LYP/ 6 311G(d ,p)水平上 ,对H2 CO和CH3 CN以及设计的 4种结构H2 CO…CH3 CN复合物等进行几何全优化和振动频率计算 ,排除振动频率为负值的非局域极小点结构 ,并对稳定的环状构型复合物结合能进行基组重叠误差校正和零点振动能校正 .分子间相互作用的能量分解分析显示 ,静电能在H2 CO…CH3 CN相互作用能量中占主导地位 ,电荷转移能居第二位 .     

Al_nCl(n=2-14)团簇结构与电子性质的理论研究

运用卡里普索(CALYPSO)结构预测方法,在杂化密度泛函B3LYP/6-311G+(d)基组水平上,对Al_nCl(n=2-14)团簇的几何结构与电子性质进行优化计算,并讨论了团簇的平均结合能、能隙、二阶能量差分、电离能、亲和能以及电子自然布居和极化率.研究结果表明:Al_nCl(n=2-14)团簇的基态构型由简单平面几何结构向立体结构演化,形成Cl原子戴帽Al_n-1Cl团簇结构;Cl原子的掺杂增大了Al_n团簇的平均结合能;二阶能量差分、能隙、电离能、亲和能的变化表明Al_7Cl是幻数团簇结构;团簇中的电荷总是由Al_原子向Cl原子转移,原子之间的成键作用随着团簇尺寸的增大而增强.     

三种低聚肽的物理化学性质的密度泛函研究

运用密度泛函理论对三种由不同氨基酸组成的低聚肽进行结构优化,并对其平均结合能和振动红外光谱进行分析,三种低聚肽分别为甘氨酸低聚肽、甘-丙氨酸低聚肽和甘-色氨酸低聚肽.本文主要研究,在肽链骨架相同而侧链基团不同的情况下,低聚肽的物理化学性质变化.结果表明,随着氨基酸残基数量的增加,三种低聚肽的结构稳定性都会增强,同时三种低聚肽也存在着尺寸效应,即官能团的振动都存在红移和奇偶振荡现象.侧链基团的引入会对低聚肽骨架的几何结构产生影响,在肽链生长过程中,侧链基团空间位阻大的分子优先自组装.本研究对应用红外光谱测定肽链基团和合成低聚肽等方面有一定指导意义.     

三种低聚肽的物理化学性质的密度泛函研究

运用密度泛函理论对三种由不同氨基酸组成的低聚肽进行结构优化,并对其平均结合能和振动红外光谱进行分析,三种低聚肽分别为甘氨酸低聚肽、甘-丙氨酸低聚肽和甘-色氨酸低聚肽.本文主要研究,在肽链骨架相同而侧链基团不同的情况下,低聚肽的物理化学性质变化.结果表明,随着氨基酸残基数量的增加,三种低聚肽的结构稳定性都会增强,同时三种低聚肽也存在着尺寸效应,即官能团的振动都存在红移和奇偶振荡现象.侧链基团的引入会对低聚肽骨架的几何结构产生影响,在肽链生长过程中,侧链基团空间位阻大的分子优先自组装.本研究对应用红外光谱测定肽链基团和合成低聚肽等方面有一定指导意义.     

Li修饰的C24团簇的储氢性能

利用密度泛函理论研究了Li原子修饰的C₂₄团簇的储氢性能. Li原子在C₂₄团簇表面的最佳结合位是五元环. Li原子与C₂₄团簇之间的作用强于Li原子之间的相互作用, 能阻止它们在团簇表面发生聚集. 当Li原子结合到C₂₄表面时, 它们向C原子转移电子后带正电荷. 当氢分子接近这些Li原子时, 在电场作用下发生极化, 通过静电相互作用吸附在Li原子周围. 在Li修饰的C₂₄复合物中, 每个Li原子能吸附两到三个氢分子, 平均吸附能处于0.08到0.13 eV/H₂范围内. C₂₄Li₆能吸附12个氢分子, 储氢密度达到6.8 wt%.     

碳硼富勒烯衍生物C18B2M(M=Li,Ti, Fe)的储氢性能计算研究

本文使用密度泛函理论(density functional theory, DFT)中的广义梯度近似(generalized gradient approximation, GGA)研究了经碱金属原子Li、过渡金属原子Ti和Fe原子修饰的富勒烯C₁₈B₂M(M=Li, Ti, Fe)的储氢性能. 研究发现, C₁₈B₂由于B的替代掺杂, 比C₂₀对金属原子具有更高的结合能. 由平均吸附能分析可知: C₁₈B₂Li对H₂的吸附能力较弱, C₁₈B₂Fe对H₂的吸附能力过强, 而C₁₈B₂Ti对H₂的平均吸附能介于0.45-0.59 eV 之间, 介于物理吸附和化学吸附之间 (0.2-0.6 eV), 因此可以实现常温下的可逆储氢. C₁₈B₂M(M=Li, Ti, Fe)能够吸附的H₂数目最多分别为4, 6和4. 由储氢机理分析可知: C₁₈B₂Li主要通过碱金属离子激发的静电场来吸附H₂, 而C₁₈B₂Ti和C₁₈B₂Fe主要通过金属原子与H₂之间的Kubas作用来吸附H₂. 由于C₁₈B₂Ti既有较大的储氢数目, 又可以实现可逆储氢, 因此有望开发成新型纳米储氢材料.     

Photoelectron spectroscopy measurements of the valence band structures of polymerized thin films of C60 and La0.1C60

The electronic valence band structures of polymerized thin films of C₆₀ and La_0.1C₆₀ have been studied by using ultra-violet photoelectron spectroscopy. Additionally, the films have been characterized by using Raman spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The valence band of the C₆₀ film shows major peaks at binding energies of 2.6, 7.2, 10.3, and 12.6 eV. In the case of the doped film, we observe (i) an additional peak with a binding energy of 13.7 eV, (ii) evidence for redistribution of the density of electronic states due to hybridization between the 5d orbitals of La and the C₆₀ cage, and (iii) significantly higher density of the electronic states near the Fermi energy. The valence band spectra of the doped film are in good agreement with recent results of the density functional theory that support strong hybridization between the d-valence orbitals of La and the C₆₀ cage.     

(TiO2)12量子环及过渡金属化合物掺杂对其电子性质影响的密度泛函理论研究

本文采用第一性原理中基于密度泛函理论(DFT)的广义梯度近似(GGA)方法, 设计了一种新的(TiO₂)₁₂ 量子环结构, 研究了它的几何结构、平均结合能及电子云分布等属性. 在此新型结构的基础上, 分别采用过渡金属化合物MoS₂, MoSe₂, MoTe₂, WS₂, WSe₂和WTe₂进行掺杂, 并分析了掺杂后体系的几何结构及电子属性(如平均结合能、能级结构、HOMO-LUMO轨道电子云密度分布和电子态密度等). 计算结果表明: (TiO₂)₁₂量子环直径为1.059 nm, 呈中心对称分布, 且所有原子组成一个二维平面结构, 使其几何结构比较稳定, 另外该量子环HOMO-LUMO轨道电子云分布均匀, 且能隙为3.17 eV, 与半导体材料TiO₂晶体的能隙的实验值(3.2 eV)非常接近. 掺杂后量子环的能隙均大幅减小, 其中WTe₂的掺杂结果能隙最小, 仅为0.61 eV, MoTe₂的掺杂结果能隙最大, 为1.16 eV, 也比掺杂前减小约2.0 eV. 其他掺杂结果的能隙都在1 eV左右, 变化不大. 这个能隙的TiO₂可以利用大部分的太阳光能, 使TiO₂具有更为广泛的应用.     

Stability and optoelectronic property of lead-free halide double perovskite Cs2B'BiI6 (B' = Li,Na and K)

Although lead-based perovskite solar cells have achieved more than 25% power conversion efficiency, the toxicity of lead and instability are still urgent problems faced in industrial application. Lead-free halide double perovskite (DP) materials are promising candidates to resolve these issues. Based on the density functional theory, we explore the geometric stability, thermodynamic stability, mechanical stability, electronic structures, and optical properties of the Cs₂B'BiI₆ (B' =m Li, Na and K) DP materials. By analyzing the tolerance factor and octahedral factor, we find the geometric stabilities of Cs₂NaBiI₆ and Cs₂KBiI₆ DPs are better than Cs₂LiBiI₆. By calculating the total energy, formation energy and decomposition energy, we propose that the most favorable structure of Cs₂B'BiI₆ is the orthorhombic phase, and Cs₂LiBiI₆ is less stable relative to the other two counterparts from an energetic viewpoint. Mechanical stability evaluations reveal that the orthorhombic Cs₂LiBiI₆ material is less stable relative to the isostructural Cs₂NaBiI₆ and Cs₂KBiI₆ DPs. The mechanical property calculations indicate that the Cs₂B'BiI₆ DPs possess good ductility, which can be used as flexible materials. Electronic structures and optical property calculations show that the orthorhombic Cs₂B'BiI₆ DPs have suitable band gap values, weaker exciton binding energies, and excellent optical absorption performance in the visible-light range. Based on the above comprehensive assessments, we can conclude that the orthorhombic Cs₂NaBiI₆ and Cs₂KBiI₆ DPs with good stability are promising candidates for solar cell applications.     

Electronic Properties of Fullerenes for Two Kinds of Hybridized Orbits

The electronic hopping energies and the band structure of a neutral C₆₀ molecule for two kinds of hybridized orbits, sp³ and sp², are studied using the Wannier function method and tight-binding approximation model, respectively. By comparison, the sp³ hybridized type is superior in the band structure obtained by employing the Wannier function method. When the effective nuclear charge number Z = 1.148 the energy gap (t_lu-h_u), bandwidth (t_3g-a_g) and threshold value (t_3g-h_u) of the ionization energy are 1.70 eV, 11.35 eV and 7.69 eV, respectively. These results are in accord with the experimental values.     

Fluorination of diamond — C4F9I and CF3I photochemistry on diamond (100)

The radiation-induced decomposition of C₄F₉I and CF₃I overlayers at 119 K on diamond (100) surfaces has been shown to be an efficient route to fluorination of the diamond surface. X-ray photoelectron spectroscopy has been used for photoactivation as well as for studying the photodecomposition of the fluoroalkyl iodide molecules, the attachment of the photofragments to the diamond surface, and the thermal decomposition of the fluoroalkyl ligands. Measured chemical shifts agree well with ab initio calculations of both C 1s and F 1s binding energies. It is found that chemisorbed CF₃ groups on diamond (100) decompose by 300 K whereas C₄F₉ groups decompose over the range 300 to 700 K and this reactivity difference is rationalized on steric grounds. Both of these thermal decomposition processes produce surface C---F bonds on the diamond. The surface C---F species thermally decompose over a wide temperature range extending up to 1500 K. Hydrogen passivation of the diamond surface is ineffective in preventing free radical attack from the photodissociated products of the fluoroalkyl iodides; I atoms produced photolytically abstract H from surface C---H bonds to yield hydrogen iodide at 119 K allowing diamond fluorination. The attachment of chemisorbed F species to the diamond (100) surface causes band bending as the surface states are occupied as a result of chemisorption. This results in a shift to higher binding energy of the diamond-related C 1s levels present in the surface and subsurface regions which are sampled by XPS on the diamond. The use of photoactivation of fluoroalkyl iodides for the fluorination of diamond surfaces provides a convenient route compared to other methods involving the action of atomic F, molecular F₂, XeF₂ and F-containing plasmas.     

A study of atomic iodine and molecular thallium iodide by X-ray photoelectron and auger electron spectroscopy

The I3d5/2 binding energy has been measured in atomic iodine, thallium iodide and cesium iodide by high temperature gas-phase photoelectron spectrscopy using Al K (1486.6 eV) X-rays. The iodine M₅N_4,5N_4,5 (¹G₄) Auger energies for TlI and CsI have also been measured and combined with binding energies to yield extra-atomic relaxation energies of 0.5 and O.3 eV, respectively, after corrections are applied to the Auger parameter. Charges were calculated using the simple potential model, which was also used to obtain an estimate of the atomic T14f binding energy. Two other estimates of the atomic T14f7/2 binding energy have also been calculated, both based on Dirac-Fock ΔSCF binding energies. The results of the three methods suggest a value of 125.3 ± 0.2 eV for T14f7/2.     

Defect induced surface chemistry: A comparison of the adsorption and thermal decomposition of C2H4 on Rh{111} and Rh{331}

The adsorption and thermal decomposition of C₂H₂ on Rh{111} is compared to the atomically stepped Rh{331} surface over a temperature range of 300 to 800 K. Using X-ray photoelectron spectroscopy (XPS) we find that the C 1s spectra as a function of C₂H₄ exposure exhibit a shift in binding energy (E_b) from 283.5 eV at 1 L C₂H₄ exposure on both surfaces to 283.8 eV on Rh{33 and to 284.1 eV on Rh{111} at saturation coverage (4 L). Careful analysis of the C 1s E_b value and full width at half maximum as a function of surface temperature after a 10 L exposure of C₂H₄ at 300 K reveals that a species consistent with a C₂H adsorbate composition is formed between 400 and 450 K on Rh{111}. This species is also observed on Rh{331} although at the lower temperature of 375 K. Computer peak deconvolution of the C 1s spectra between 500 and 700 K suggests that a CH_ads or C_ads surface fragment is formed and increases in concentration at the expense of the C₂H species as the surface temperature increases. Above 750 K a graphite overlayer is formed on both surfaces. This overlayer, however, exhibits a low degree of carbon π-character bonding on Rh{331}. The adsorption and decomposition mechanisms suggest that the 300 K C₂H₄ adsorbate on Rh{331} is ethylidyne and that the stepped surface is more thermally reactive than the flat Rh{111} surface.     

ELECTRONIC STRUCTURE STUDIES OF THE C60 FILM CONDENSED ON 2H-MoS2(0001) SURFACE

The electronic structure and vibrational spectrum of the C₆₀ film condensed on a 2H- MoS₂(0001) surface have been investigated by X-ray photoelectron spectroscopy (XPS), ul-traviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES) and infrared high-resolution electron-energy-loss spectroscopy (HREELS). AES analysis showed that at low energy side of the main transition, C₆₀ contains a total of three peaks just like that of graphite. However, the energy position of the KLL main Auger transition of C₆₀ looks like that of diamond, indicating that the hybridization of the carbon atoms in C₆₀ is not strictly in sp²- bonded state but that the curvature of the molecular surface introduces some sp²pz- bonded character into the molecular orbitals. XPS showed that the C 1s binding energy in C₆₀ was 285.0eV, and its main line was very symmetric and offered no indication of more than a single carbon species. In UPS measurement the valence band spectrum of C₆₀ within 10eV below the Fermi level (E_F) shows a very distinct five-band structure that character-izes the electronic structure of the C₆₀ molecule. HREEL results showed that the spectrum obtained from the C₆₀ film has very rich vibrational structure. At least, four distinct main loss peaks can be identified below 200 meV. The most intense loss was recorded at 66 meV, and relatively less intense losses were recorded at 95, 164 and 197meV at a primary energy of electron beam E_P = 2.0eV. The other energy-loss peaks at 46, 136, 157 and 186meV in HREEL spectrum are rather weak. These results have been compared to infrared spectrum data of the crystalline solid C₆₀ taken from recent literatures.