Chromophores of neutral and dicationic thiophene-based oligomers – A study by first-principle methods

Time-dependent density functional theory (TD-DFT) and semiempirical methods (ZINDO-CIS, PPP-CIS) were applied to colored neutral and dicationic thiophene-based oligomers; in addition to the parent oligothiophenes and various ,′-end-capped derivatives, oligothiophenes with thiophene rings linked by methine, vinylene or phenylene groups were studied. Being π-chromophores, the compounds absorbed intensely in the Vis–NIR region; variation of the absorption energy with the reciprocal of the number of thiophene rings resulted in low band gap (as is known for low band gap polymers). Whilst the parent oligothiophenes displayed no singlet/singlet instability up to the octadecithiophene, the long chain oligomers were singlet/triple unstable. According to BS-UDFT calculations, biradical oligomers (two-plarons) were slightly favored over conventional dications (bipolarons). The color-determining electronic transitions of large size oligothiophenes calculated by open shell TD-DFT were little shifted in energy relative to those calculated using closed shell TD-DFT. The electronic structure of the oligomers is discussed in terms of bond length alternation and nucleus-independent chemical shifts.     

溶胶凝胶法制备的La_（2–x）M_xCuO_（4–δ）晶体的UV–Vis–NIR光学性质

采用溶胶–凝胶法制备了La2CuO4和La2–xMxCuO4–δ（M=Ca、Sr和Ba）晶体。通过X射线衍射、扫描电子显微镜和紫外–可见–近红外光谱对La2CuO4和La2–xMxCuO4–δ（x=0.1）粉体进行了测试和表征。结果表明,700℃煅烧2h,可以获得单相La2CuO4和La2–xMxCuO4–δ（M=Ca、Sr和Ba）,且均为正交晶型结构。光谱性质表明,La2CuO4和La2–xMxCuO4–δ系化合物在紫外–可见和近红外范围都有较宽的吸收。La2CuO4、La1.9Ca0.1CuO4–δ、La1.9Sr0.1CuO4–δ和La1.9Ba0.1CuO4–δ的带隙分别为1.44、1.57、1.40eV和1.37eV。带隙的变化是由于碱土金属离子的半径不同,造成对键的不匹配性的影响不同而引起的。     

溶胶凝胶法制备的La2–xMxCuO4–δ晶体的UV–Vis–NIR光学性质（英文）

采用溶胶–凝胶法制备了La2CuO4和La2–xMxCuO4–δ(M=Ca、Sr和Ba)晶体。通过X射线衍射、扫描电子显微镜和紫外–可见–近红外光谱对La2CuO4和La2–xMxCuO4–δ(x=0.1)粉体进行了测试和表征。结果表明,700℃煅烧2 h,可以获得单相La2CuO4和La2–xMxCuO4–δ(M=Ca、Sr和Ba),且均为正交晶型结构。光谱性质表明,La2CuO4和La2–xMxCuO4–δ系化合物在紫外–可见和近红外范围都有较宽的吸收。La2CuO4、La1.9Ca0.1CuO4–δ、La1.9Sr0.1CuO4–δ和La1.9Ba0.1CuO4–δ的带隙分别为1.44、1.57、1.40 eV和1.37 eV。带隙的变化是由于碱土金属离子的半径不同,造成对键的不匹配性的影响不同而引起的。     

Understanding the Electronic Structure of Larger Azaacenes through DFT Calculations

Although azapentacenes have been widely demonstrated as promising candidates for n-type organic semiconductor devices, the exploration of larger azaacenes is still a challenge. In particular, theoretical studies on the electronic structures of larger azaacenes and the influence of N substitution on the ground states are still rare. Herein, we reported our investigation on the electronic ground-state characters of larger azaacenes through density functional theory (DFT) calculations. Our results indicated that larger azaacenes (fused aromatic rings larger than 6) would show open-shell singlet biradical characters and the introduction of more N atoms into the backbone of large acenes could favor their closed-shell ground states. Interestingly, azahexacenes with three or more N atoms (compounds N64–N68) and azaheptacenes (compound N74) with fourteen N atoms displayed closed-shell singlet ground states compared with the open-shell singlet diradical ground states for larger acenes. Our theoretical studies may guide the design and synthesis of larger azaacenes, which are the promising n-type organic semiconducting materials.     

Keggin型多阴离子[XW_(12)O_(40)]~(n-)(X=Si,Ge,P,As)电子性质的密度泛函理论研究

采用密度泛函理论方法研究了Keggin型多阴离子[XW12O40]n-(X=Si,Ge,P,As)的电子性质,在几何优化基础上,分析杂原子对体系的几何结构,电子性质,氧化还原性质的影响。结果表明:杂原子对多阴离子的键长有影响,变化规律与杂原子半径递变一致;杂原子的电子性质影响多阴离子的氧化性,多阴离子的氧化能力随杂原子的电负性增大而提高;杂原子的核电荷数越大,该多阴离子的氧化性越强;多阴离子的酸强度与杂原子的电负性次序一致。     

Excited States Computation of Models of Phenylalanine Protein Chains: TD-DFT and Composite CC2/TD-DFT Protocols

The present benchmark calculations testify to the validity of time-dependent density functional theory (TD-DFT) when exploring the low-lying excited states potential energy surfaces of models of phenylalanine protein chains. Among three functionals suitable for systems exhibiting charge-transfer excited states, LC-ωPBE, CAM-B3LYP, and ωB97X-D, which were tested on a reference peptide system, we selected the ωB97X-D functional, which gave the best results compared to the approximate coupled-cluster singles and doubles (CC2) method. A quantitative agreement for both the geometrical parameters and the vibrational frequencies was obtained for the lowest singlet excited state (a ππ* state) of the series of capped peptides. In contrast, only a qualitative agreement was met for the corresponding adiabatic zero-point vibrational energy (ZPVE)-corrected excitation energies. Two composite protocols combining CC2 and DFT/TD-DFT methods were then developed to improve these calculations. Both protocols substantially reduced the error compared to CC2 and experiment, and the best of both even led to results of CC2 quality at a lower cost, thus providing a reliable alternative to this method for very large systems.     

Excited-state nature in benzodifuranone dyes: Insights from ab initio simulations

Using ab initio theoretical tools simultaneously accounting for electron correlation and environmental effects, we have simulated the optical spectra of benzodifuranone dyes. In a first step, a valuable computational protocol has been defined and it turned out that a PCM-TD-M06-2X/6-311+G(2d,p)//PCM-PBE0/6-311G(d,p) approach provides an adequate balance between computational requirements and accuracy (deviations of ca. 10 nm with respect to experiment). In a second stage, we have calculated the spectrum of a large series of push-pull structures, and it turned out that the benzodifuranone core is a strong electron capturing group at the excited-state. Indeed, strong auxochroms like the nitro and cyano groups fall short to significantly perturb the LUMO of this series of chromogens. Eventually, in a last phase, the implications of these results are discussed for a series of organic dyes of potential interest for solar cells (DSSC).     

药物合成中间体5-甲氧基吲哚的DFT研究

用密度泛函理论（DFT）B3LYP方法，取3-21G、6-31G^＊、6-311G^＊、6-311G^＊＊4种基组，通过能量梯度全优化分别计算研究了5-甲氧基吲哚的分子几何构型和电子结构，发现除了甲氧基上的氢，其它所有原子均在一个平面上。并在B3LYP／6-311G^＊＊水平上对全优化的几何构型进行简正振动频率分析，给出了各种频率所对应的红外强度，并对上述计算结果进行了比较和讨论。     

Phase transformations in the relaxor Na1/2Bi1/2TiO3 studied by means of density functional theory calculations

The relaxor material Na_1/2Bi_1/2TiO₃ (NBT) is an important basis for the development of lead‐free piezoceramics, but still many features of this material are not well understood. Here, we study the kinetics of phase transformations by octahedral tilts and A‐cation displacements in NBT by means of density functional theory calculations, employing ab initio molecular dynamics and nudged elastic band calculations. Our results show that the energetic differences between the low temperature rhombohedral, intermediate orthorhombic and other metastable phases are close to the room temperature thermal energy. Therefore, it is likely that above room temperature, several octahedral tilt patterns are present simultaneously on the local scale, just because of thermal vibration of the oxygen ions. Octahedral tilt transformations and A‐cation displacements show similarly high energy barriers, however, since the vibrational frequency of oxygen is higher, tilt transformations occur more frequently. Further, tilt transformations in which the oxygen octahedra get deformed the least are more probable to occur. We also find that the chemical A‐cation order affects energy barriers, influences the coupling between rotational and displacive modes and determines the stability of certain octahedral tilt orders. We conclude that the so‐called polar nanoregions in this material result from local octahedral tilt transformations and subsequent A‐cation displacements, which are driven by thermal vibration and are mediated by the underlying chemical order.     

A Magic-Angle-Spinning NMR Spectroscopy Method for the Site-Specific Measurement of Proton Chemical-Shift Anisotropy in Biological and Organic Solids

Proton chemical shifts are a rich probe of structure and hydrogen-bonding environments in organic and biological molecules. Until recently, measurements of ¹H chemical-shift tensors have been restricted to either solid systems with sparse proton sites or were based on the indirect determination of anisotropic tensor components from cross-relaxation and liquid-crystal experiments. We have introduced a magic-angle-spinning approach that permits site-resolved determination of chemical-shift-anisotropy tensors of protons forming chemical bonds with labeled spin 1/2 nuclei in fully protonated solids with multiple sites, including organic molecules and proteins. This approach, originally introduced for the measurements of chemical-shift tensors of amide protons, is based on three RN-symmetry-based experiments, from which the principal components of the ¹H chemical-shift tensor can be reliably extracted by simultaneous triple fit of the data. Herein, we expand our approach to a much more challenging system involving aliphatic and aromatic protons. We start with a review of prior work on experimental NMR spectroscopy and computational quantum chemical approaches for measurements of ¹H chemical-shift tensors and relating these to the electronic structures. We then present our experimental results on U-¹³C,¹⁵N-labeled histidine and demonstrate that ¹H chemical-shift tensors can be reliably determined for the ¹H¹⁵N and ¹H¹³C spin pairs in cationic and neutral forms of histidine. Finally, we demonstrate that the experimental ¹H(C) and ¹H(N) chemical-shift tensors are in agreement with DFT calculations; therefore, establishing the usefulness of our method for the characterization of structures and hydrogen-bonding environments in organic and biological solids.     

Characterization of functional states in nicotine‐ and cotinine‐imprinted poly(4‐vinylphenol) films by nanoindentation

Thin, imprinted poly(4‐vinylphenol) (PVP) films were produced by spin coating using nicotine or its metabolite, cotinine, as template molecules. The template molecules were extracted from these films and later reloaded (or cross‐loaded) from solution. Depth sensing nanoindentation was applied to measure the nanomechanical properties of the imprinted polymer films. Changes in the nanomechanical properties were correlated to the functional state of the imprinted polymer, allowing identification of the films in their “as produced” state, “template removed state or “reloaded” state. In addition, the nanomechanical properties were capable of identifying which of the two template molecules were inserted in to a film. Reinsertion of a template molecule into a “template removed” film was found to increase the nanohardness over the values recorded for the “as produced” film. This behavior was discussed in terms of the hydrogen bonding characteristics of the materials (through density functional calculations) and the physical properties of poly(4‐vinylphenol) coatings. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A theoretical investigation on the properties of the new poly(N‐vinylcarbazole)‐3‐methylthiophene (PVK‐3MeT) synthesized graft copolymer

In this article, we present quantum chemical calculations, based on density functional theory (DFT), performed to investigate the geometries and the opto‐electronic properties of a new synthesized graft copolymer based on poly(N‐vinylcarbazole) (PVK) and poly(3‐methylthiophene) (PMeT) named PVK‐3MeT. First, we have theoretically computed and compared the structural, optical, and vibrational parameters of both neutral and doped states. In addition, the excited state was theoretically obtained by the ab initio RCIS/STO‐3G method. To assign the absorption and emission peaks observed experimentally, we computed the energies of the lowest singlet excited state with the time‐dependent density functional theory (TD‐DFT) method. Electronic parameters such as the HOMO‐LUMO band gap, the ionization potential (IP), and electron affinity (EA) are extracted. Calculations show that the PVK‐3MeT copolymer is nonplanar in its ground neutral state. Meanwhile, upon doping or photoexcitation, an enhancement of the planarity is observed, resulting on a decrease of the inter‐ring torsion angle between 3‐methylthiophene units. Such modifications in the geometric parameters induce a dramatic change on the HOMO and LUMO orbitals in the doped or excited states. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Zn3V2O8的电子结构与光学性质的理论研究

采用平面波超软赝势密度泛函理论的方法研究了Zn3V2O8的能带结构、电子态密度和光学特性.能带结果显示Zn3V2O8呈间接带隙的绝缘体型能带,其禁带宽度为2.9 eV.详细的电子态密度结果显示其费米面上的态密度达到20 e/eV,费米能级附近的能级由Zn3p、V3p和O2p电子形成,Zn3d和O2s之间有强的杂化作用.介电性能结果显示在4.4 ～5.7 eV附近有强的吸收峰,在20.6 eV附近有一个次强吸收峰;吸收光谱显示在6.8 eV处有强吸收,在20.7 eV处有一个较弱的吸收峰.     

CdGeAs2晶体的结构、弹性和电子性能的模拟计算和分析

利用基于密度泛函理论的平面波赝势法对CdGeAs2晶体的结构,弹性和电子性能进行了研究.CdCeAs2晶体具有6个独立的弹性常数,利用计算的弹性性能可以判断晶体具有机械稳定性、延性和弹性各向异性等力学特点.通过总的和部分态密度分析了不同能带的贡献成分.计算的结构参数及弹性常数与实验值基本吻合.CdGeAs2晶体具有直接...     

Vibrational Spectra and Molecular Vibrational Behaviors of Dibenzyl Disulfide,Dibenzyl Sulphide and Bibenzyl

The vibration spectroscopy (Raman and infrared) of widely concerned molecules in sulfur corrosion phenomenon (Dibenzyl Disulfide, Dibenzyl Sulphide, and Bibenzyl) is detailedly analyzed based on density functional theory and experimental measurement. The dominant conformations of these molecules are determined according to Boltzmann distribution in relative Gibbs free energy. Additionally, noncovalent interaction analysis is conducted to indicate intramolecular interaction. Vibration normal mode is assigned based on potential energy distribution, which comprehensively reveals the molecular vibrational behaviors. Conformations weighted spectra are obtained and compared with experimentally measured spectra. We found that experimental spectra are in good agreement with the theoretical spectra in B3LYP-D3(BJ)/6-311G** level with a frequency correction factor. Furthermore, the divergence among these molecules is discussed. The vibrational behavior of the methylene group in the molecule shows a trend with the presence of the sulfur atom.     

Structural,electronic, and dielectric properties of a large random network model of amorphous zeolitic imidazolate frameworks and its analogues

The amorphous zeolitic imidazolate frameworks (a-ZIFs) models and its analogues (with 918 or 810 atoms, respectively) are constructed based on a larger continuous random network (CRN) model of amorphous SiO₂ (a-SiO₂) model. The atomic, electronic, and dielectric properties of these structures, which possess different metal nodes and organic linkers, are investigated by well-defined density functional theory (DFT) calculations. The results suggest that all a-ZIFs have ultra-low dielectric constants and a large energy loss function (ELF), which suggests that they may be good candidates for electromagnetic absorptive materials. Most important, these a-ZIFs models offer a base-line model for other amorphous ZIFs for further research on models containing vacancies, defects, doping or under high pressure or high temperature.     

Pt/Au(111)表面合金电化学稳定性的第一性原理研究

利用密度泛函理论(DFT)对Pt/Au (111)表面合金的电化学稳定性进行了初步研究。形成能计算结果表明,Au与Pt不易在块体中形成合金,但能在Pt (111)面形成表面合金。溶解电位计算结果进一步表明,Pt/Au (111)面上Pt原子的溶解电位与其第一近邻Au原子数有很好的线性关系,而Au对第二近邻及更远近邻的Pt溶解电位的影响可忽略。这些结果意味着可建立表面配位环境与表面原子溶解电位间的标度关系,为揭示表面合金的结构-电化学稳定性构型关系奠定了基础。     

二维AuP2材料电催化固氮性能的理论研究

通过电化学反应将氮气（N₂）和水（H₂O）在常温常压的条件下转化为氨气（NH₃）是一种绿色环保的合成氨方法。但由于N₂具有非常高的化学惰性,必须借助电催化剂来加速反应的动力学过程。通过密度泛函理论计算揭示出新型二维无机材料AuP₂对N₂电化学还原制NH₃具有很好的催化活性。在二维AuP₂材料中,Au与P之间由于电负性差异发生显著的电荷转移,使带有正电荷的P可作为活性位点促进氮还原。计算表明整个反应的速控步是N₂生成^*NNH的过程,限制电压为1.2 V,催化活性可以跟部分金属催化剂相媲美。为设计高效氮还原电催化剂提供了新的思路。