Computational study of diketopyrrolopyrrole-based organic dyes for dye sensitized solar cell applications

Four diketopyrrolopyrrole (DPP)-based organic dyes utilizing the donor–π-acceptor motif were investigated by density functional theory (DFT) and time-dependent DFT (TDDFT) approaches. The four dyes were composed of different donor groups, i.e. indoline, carbazole, triphenylamine, and coumarin. We investigated the effects of the DPP unit and different donors on the spectra and electrochemical properties of the dyes, respectively. In comparison with the model dye which adopts a phenylene unit as the π-spacer, the DPP dyes all display remarkably enhanced spectral responses in the visible region of the solar spectrum. The key to this increase was the incorporation of electron-deficient DPP moieties to the molecular core, which significantly lowers LUMO levels and therefore reduces the band gap. The dye/(TiO₂)₄₆ anatase nanoparticle systems were also simulated to show the electronic structures at the interface. We studied some key properties including absorption spectra, light-harvesting efficiency, molecular orbital distributions, and injection time of electrons from the excited state of dye to the conduction band of TiO_2. The dye DPP-I with indoline moiety as the electron donor demonstrates desirable energetic, electronic, and spectroscopic parameters for dye sensitized solar cells (DSSCs) applications. Our theoretical study is expected to provide valuable insights into the molecular design of novel DPP-based organic dyes for the optimizations of DSSCs.     

The effect of different π-bridge configuration on bi-anchored triphenylamine and phenyl modified triphenylamine based dyes for dye sensitized solar cell (DSSC) application: A theoretical approach

Twenty eight bi-anchored triphenylamine (TH-1 to TH-14) and phenyl modified triphenylamine (PH-TH-1 to PH-TH-14) based metal free organic dyes are designed for DSSC application. The electronic effect of different π-bridge configurations in donor-π-bridge-acceptor (D-π-A)₂ structure was theoretically simulated and verified using density functional theory (DFT) and time dependent density functional theory (TD-DFT). The triphenylamine and phenyl modified triphenylamine groups are used as donor and cyanoacrylic acid group is used as acceptor. Thiophene and cyanovinyl groups are used as π-bridge. The ground state molecular structure was optimized by density functional theory and the electronic absorption spectra were calculated by time dependent density functional theory. The light harvesting efficiency (LHE), dye regeneration energy (ΔG_reg) and electron injection energy (ΔG_inject) are determined by computational examination. It is observed that, when the number of π-bridge increases, the band gap of the dye decreases. Also the absorption maximum and molar extinction coefficient of the dyes are increased. Theoretical result shows that the thiophene-cyanovinyl and thiophene-thiophene-cyanovinyl–cyanovinyl configurations give broader and red shifted absorption spectrum compared to other configurations. Also the results of phenyl modified triphenylamine (PH-TH) dyes clearly show better absorption and dye regeneration energy compared to TH dyes.     

Quantum mechanical description of the interactions between DNA and water

In recent years, a lot of attention has been focused on the electronic properties of DNA. With recent advances in linear scaling quantum mechanics there are now new tools available to enhance our understanding of the electronic properties of DNA among other biomolecules. Using both explicit solvent models and implicit (continuum) solvent models, the electronic characteristics of a dodecamer duplex DNA have been fully studied using both divide and conquer (D&C), semi-empirical quantum mechanics and non-D&C semi-empirical quantum mechanics. According to the AM1 Hamiltonian, 3.5 electrons (0.3 electron/base pair) are transferred from the duplex to the solvent. According to the density of state (DOS) analysis, in vacuo DNA has a band gap of 1 eV showing that in the absence of solvent, the DNA may exhibit similar properties to those of a semiconductor. Upon increasing solvation (2.5–5.5 Å), the band gap ranges from 3 eV to 6 eV. For the implicit solvent model, the band gap continues this widening trend to 7 eV. Therefore, upon solvation and in the absence of dopants, the DNA should begin to loose its conductive properties. Finally, when one considers the energy and localization of the frontier orbitals (HOMO and LUMO), solvent has a stabilizing effect on the DNA system. The energy of the HOMO drops from 15 eV in vacuo to 2 eV for 5.5 Å of water to −8 eV for the implicit solvent model. Similarly, the LUMO drops from 16 eV for in vacuo to 9 eV for 5.5 Å of water to −1 eV for the implicit model. Beyond the importance of the computed results on the materials properties of DNA, the present work also shows that the behavior of intercalators will be affected by the electronic properties of DNA. This could have an impact on our understanding of how DNA based drugs interact with DNA and on the design of new DNA based small molecule drugs.     

Synthesis and characterization of novel blue azo‐dye derivatives containing acrylate group for dye‐based color filters

Abstract— Even though dyes have a fine resolution and good chromaticities, they are not widely used as coloring materials for color filters (CFs) due to their low thermal stability and chemical resistance. A series of azo‐dye derivatives, which consist of two cross‐linkable acrylate or methacrylate groups to improve thermal and chemical properties, have been synthesized and used to fabricate color filters. The spectral properties and chemical/thermal stabilities of the fabricated CFs were investigated by comparing dye‐based CFs, without a complicated dispersion process, but with pigment‐based CFs using dispersed pigment. Also, more properties including the development test and surface morphologies lithographic properties were studied. The synthesized azo dyes were characterized by elemental analysis, UV‐visible spectra, IR, mass, and ¹H‐NMR spectra.     

还原型牛红细胞Cu(I)Zn-SOD的量化计算

运用G94W量子化学程序,在B3YIP/Lan12dz基组的水平上,对于还原型牛红细胞中CU(I)Zn-SOD活性中心进行了从头计算。研究了分子轨道能量,电荷分布,前线轨道的贡献。结果表明:前沿分子轨道能量均为负值,其电子光谱稳定,与金属配位的咪唑环电荷表现正负交替现象。在前线轨道贡献上Cu(I)的占有轨道贡献大,空轨道的贡献小,不易于接受O_O~-自由基的不成对电子。     

乙二胺缩3,5-二氯水杨醛的合成、表征及量子化学计算

本文用乙二胺与水杨醛衍生物在非水相中合成了一种新的双希夫碱配体,并通过元素分析、核磁、质谱和红外等方法进行了表征。采用Gaussian 03在DFT/B3LYP水平下进行理论研究。计算出分子总能量TE、分子最高占据轨道能E_(HOMO)、分子最低空轨道能E_(LUMO)、标准焓H~θ、标准自由能G~θ、恒容热熔Cv~θ、标准熵S~θ、零点能E_0、分子偶极矩μ、前线轨道能量差△E等热力学参数。优化了几何构型模拟出分子的部分重要键长((?))、键角(°)、二面角(°)等结构参数。经过Mulliken布居分析得到了原子的净电荷分布。计算出原子轨道对前线分子轨道的贡献(%)。通过对热力学参数、结构参数、原子净电荷布局和原子轨道对前线分子轨道贡献的总体探讨,表明目标分子具有较好的空间结构和较强的配位能力,是一个良好的配体;并且,它的生物活性很强,可以进一步进行抑菌性能和抗氧化性能等研究并且应用到各个领域。     

Extending donor size in D-A-π-A organic dye for dye sensitized solar cells: Anti-aggregation and improving electron injection

We have theoretically designed two D-A-π-A dyes 3 and 4 based on the efficient references 1 and 2 by introducing an extra electron donor unit (D2). Via calculating the electronic structures of isolated dyes, we obtain that dyes 3 and 4 possess stronger light-harvesting efficiency imparted by the fluorescence energy transfer of D2 part, maintain comparable lifetime of excited states, and shorten the electron injection time significantly with regard to 1 and 2. Meanwhile, dye 3 positively shifts the edge of virtual states of TiO₂ in a larger extent compared to its counterparts. Then after considering the alignment morphology of multiple dyes adsorbed on TiO₂ surface, we find that dyes 3 and 4 manifest the capability of anti-aggregation obviously, which is evidenced by the smaller quantity of intermolecular electronic coupling compared to that of dyes 1 and 2, definitively illustrating the prominent performance of novel dyes with the bulky D2 moiety. Finally, dye 3 is screened out as the potential candidate for future application.     

Quantum mechanical description of the interactions between DNA and water

In recent years, a lot of attention has been focused on the electronic properties of DNA. With recent advances in linear scaling quantum mechanics there are now new tools available to enhance our understanding of the electronic properties of DNA among other biomolecules. Using both explicit solvent models and implicit (continuum) solvent models, the electronic characteristics of a dodecamer duplex DNA have been fully studied using both divide and conquer (D&C), semi-empirical quantum mechanics and non-D&C semi-empirical quantum mechanics. According to the AM1 Hamiltonian, ∼3.5 electrons (∼0.3 electron/base pair) are transferred from the duplex to the solvent. According to the density of state (DOS) analysis, in vacuo DNA has a band gap of ∼1 eV showing that in the absence of solvent, the DNA may exhibit similar properties to those of a semiconductor. Upon increasing solvation (2.5–5.5 Å), the band gap ranges from ∼3 eV to ∼6 eV. For the implicit solvent model, the band gap continues this widening trend to ∼7 eV. Therefore, upon solvation and in the absence of dopants, the DNA should begin to loose its conductive properties. Finally, when one considers the energy and localization of the frontier orbitals (HOMO and LUMO), solvent has a stabilizing effect on the DNA system. The energy of the HOMO drops from ∼15 eV in vacuo to ∼2 eV for 5.5 Å of water to ∼−8 eV for the implicit solvent model. Similarly, the LUMO drops from ∼16 eV for in vacuo to ∼9 eV for 5.5 Å of water to ∼−1 eV for the implicit model. Beyond the importance of the computed results on the materials properties of DNA, the present work also shows that the behavior of intercalators will be affected by the electronic properties of DNA. This could have an impact on our understanding of how DNA based drugs interact with DNA and on the design of new DNA based small molecule drugs.     

新型咔唑衍生物密度泛函理论的研究

运用量子化学中的密度泛函和含时密度泛函理论法,计算1种新型咔唑衍生物,以探讨其几何构型、电子结构、前线分子轨道和电子光谱性质。计算结果表明当2-(4-吡啶基)乙烯基的反式构型与咔唑环作用时比顺式稳定,引入取代基后使化合物的HOMO和LUMO之间的能隙降低,吸收光谱红移。电子被激发时,电子从咔唑环向吡啶环转移,说明新型咔唑类化合物具有很好的光学性能,可以作为空穴传输材料。     

TTF-C60-P衍生物的分子结构和光谱性质的理论研究

用半经验AMI法研究TTF-C60-P衍生物的分子轨道,电荷分布,几何构型。计算结果显示,TTF-C60-P衍生物具有较低的跃迁能。HOMO轨道主要分布在杂环上,LUMO轨道则主要分布在C60上。电荷从富电子的TTF向缺电子体C60转移。理论预测TTF-C60-P衍生物在基态下产生长寿命的电荷分离态。     

Fibre-optic evanescent sensing of gaseous ammonia with two forms of a new near-infrared dye in comparison to phenol red

We report the evanescent detection of gaseous ammonia using the methylated and ethylated forms of a new dye and comparing their performance to that of the indicator dye phenol red. The two forms of the new dye were developed to produce spectral changes in the near-infrared region of the spectrum. Each of the dyes have been immobilised into the cladding material of commercial available plastic-clad silica (PCS) fibre. The response to gaseous ammonia was maximum at 565 nm for phenol red and 735 and 744 nm for the methylated and ethylated forms of the copper complex, respectively, and the calibration curves for the three dyes investigated exhibit a dynamic range of three orders of magnitude. Although all sensing fibres showed reversible responses to ammonia, the responses times were slow and need improving. The effect of atmospheric moisture on the copper complex methylated form was found to be negligible in the range of 0–50%RH.     

N-甲基-2-(5-甲基-噻吩)-吡咯并[3,4]C60(MTPC)衍生物的分子结构和几何构型的理论研究

用半经验AM1法研究N-甲基-2-(5-甲基,噻吩)-吡咯并[3,4]C_(60)(MTPC)衍生物的分子轨道,电荷分布,几何构型。计算结果显示,分子(C)具有较低的跃迁能。HOMO轨道主要分布在杂环上,LUMO轨道则主要分布在C_(60)上。电荷从富电子的噻吩环向缺电子体C_(60)种转移。预测(C)可能在基态下产生长寿命的电荷分离态。     

Chip making to dye for

A University of Washington researcher is using common food dyes to improve photolithography, the dominant semiconductor microfabrication technology. The microfluidic masks are made by filling transparent silicone channels with red dye, which blocks UV light, to create the desired patterns to be projected onto the photoresist.     

Quantum mechanical investigations on the role of C-terminal residue in influencing the structural features of dipeptides containing N-terminal proline

This study investigates the influence of the side chain moiety of C-terminal residue on the structural and molecular properties of seven dipeptides having proline at their N-terminal positions. The C-terminal component of the dipeptides is varied with seven different combinations viz. Ala, Leu, Asp, Thr, Asn, Arg and Sec. The calculations are carried out using B3LYP/6-311++G(d,p) level of theory in gas and implicit aqueous phase. Effects of explicit aqueous environment on the dipeptide structures are also investigated for two systems. The results furnished by this DFT study provide valuable information regarding the role of the side chain groups of C-terminal residues in determining the structural features of the amide planes, values of the ψ and ф dihedrals, geometry about the α-carbon atoms, theoretical IR spectra as well as the number and type of intramolecular H-bond interactions existing in the dipeptides, and extend a fine corroboration to the earlier theoretical and experimental observations. In aqueous phase the dipeptide geometries exhibit larger values of total dipole moments, greater HOMO–LUMO energy gaps and enhanced thermodynamic stability than those in gas phase. The explicit water molecules are found to modify the geometrical parameters related to the amide planes and vibrational spectra of the dipeptides.     

Azo‐dye aligning layers for liquid‐crystal cells

Abstract— The photo‐induced alignment of liquid crystal onto a photochemical stable azo‐dye film was studied for liquid‐crystal display (LCD) applications. The photo‐aligning of azo dye takes place due to the pure reorientation of the molecular absorption oscillators perpendicular to the UV‐light polarization. The order parameters S = ?0.4 (80% of the maximum absolute value S_m = ?0.5) was measured at a wavelength of 372 nm from the polarized absorption spectra. The temperature‐stable pretilt angle of 5.3° was obtained by a two‐step exposure of azo‐dye film using normally incident polarized light followed by oblique non‐polarized light. The azimuthal anchoring energy of the photo‐aligned substrate was A_? > 10^?4 J/m², which is of the same magnitude as the anchoring of the rubbed PI layer. The VHR value of the photo‐aligned LC cell was also found to be very high (98–99%) at room temperature and more than 95% at T=80°C. The thermal stability of the photo‐aligned azo‐dye layers is sufficiently high, while UV stability has to be improved, _e.g., by polymerization. The new LCD aligning technology based on photochemical stable azo‐dye layers is envisaged.     

桂皮酰哌啶类化合物结构与抗惊活性关系的量子化学研究

利用量子化学从头算方法，对13种桂皮酰哌啶类化合物的结构与抗惊生物活性关系进行了研究。采用限制性Hartree-Fock(RHF)方法和6-31G基组，对13种化合物进行全参数优化，得到了它们的稳定构型。并对前线分子轨道能级、轨道组成等性质进行了分析，把它们与实验得到的生物活性参数进行了相关分析，并对某些参量进行了线性回归，得到了回归方程。通过研究发现，桂皮酰哌啶类化合物的抗惊生物活性与分子的前线轨道(HOMO、LUMO)能级和轨道组成存在一定的相关性。通过轨道组成分析发现，具有较高生物活性的分子，其HOMO、LUMO轨道中羰基和烯键所占的比重较大，说明羰基和烯键部位应为此类化合物的活性部位。     

A CALPHAD-type Young's modulus database of Ti-rich Ti–Nb–Zr–Mo system

Accurate Young's modulus is the necessity for the design of biomedical Ti alloys. A combinatorial method of the diffusion couple, nanoindentation, electron probe microanalysis (EPMA), and CALculation of PHAse Diagrams (CALPHAD) techniques has been utilized to construct the Young's modulus database of Ti alloys with various compositions in the present work. Two groups of body-centered cubic (bcc) Ti–Nb–Zr–Mo quaternary diffusion couples annealed at 1273 K for 25 h were experimentally prepared. Subsequently, the composition-dependent mechanical properties in the wide compositional range of Ti-based alloys were obtained by using EPMA and nanoindentation probes. Finally, on the basis of the measured Young's moduli in the present and previous work and the modeling parameters of Young's modulus of Ti–Nb–Zr system, the Young's modulus database of bcc Ti–Nb–Zr–Mo system was established through the CALPHAD approach. The CALPHAD-type database of bcc Ti–Nb–Zr–Mo system can provide the accurate Young's moduli of Ti alloys with wide compositions.     

DFT simulation towards evaluation the molecular structure and properties of the heterogeneous C16Mg8O8 nano–cage as selective nano–sensor for H2 and N2 gases

Adsorption of hydrogen (H₂) and nitrogen (N₂) molecules was analyzed on a new fullerene–like C₁₆Mg₈O₈ nano–cage, composed of magnesium, oxygen, and carbon, using density functional theory. A detailed analysis of the energy, geometry, and electronic structure of various H₂ and N₂ adsorptions on the cluster surface was performed. The adsorption energies of H₂ and N₂ were estimated to ranging from −0.16 to −0.52 eV, respectively. The most stable adsorption configurations were those in which the H or N atoms of the adsorbates were located near the Mg atom of the cluster surface at different sides. It was found that the heterogeneous C₁₆Mg₈O₈ nano–cluster selectively act against the H₂ and N₂ gaseous molecules. The electrical conductivity of the cluster, arising from HOMO/LUMO energy gap, was more sensitive to N₂ gaseous molecule rather than H₂ one, indicating that the heterogeneous C₁₆Mg₈O₈ nano–cage may be potential nano–sensor for N₂ molecule. These findings were specified by analyzing the characteristics in the electron density of states (DOS).