Photoinduced electron transfer across linearly fused oligo-norbornyl structures

The rates of photoinduced electron transfer (ET) reactions across two oligo-norbornyl spacer groups (S), that is, structure 1 fused by two norbornadiene (NBD) units and structure 2 fused by three NBD units, are examined. Substituted naphthalene acted as an electron donor (D), whilst ethylene-1,2-dicarboxylate as an electron acceptor (A). ET rates were measured by fluorescence quenching experiments on these D-S-A dyads, and the results were correlated with reaction free energies according to the Marcus relationship. It was found that naphthalene with phenyl substituents showed relatively slower ET rates. The conformational flexibility of phenyl substituents may cause a hindrance on the electronic coupling between D and A. Another salient feature was the abnormally high quenching rates observed in nonpolar solvents such as cyclohexane, the results of which may be ascribed to a competing energy transfer process.     

Modeling high-pressure densities at wide temperature range with volume scaling: Cyclohexane + n-hexadecane mixtures

High-pressure density data for cyclohexane + n-hexadecane mixtures at a wide temperature range was modeled with several classical equations of state (EOS) and correlative models. A modification for softening the co-volume and another for a volume scaling of the Peng–Robinson EOS (VS-PR) were proposed. The VS-PR model is able to correlate the pure component experimental data employing only five adjustable parameters, with root-mean-square deviation (RMSD) between calculated and experimental densities essentially within the experimental error. This result is superior to widely used approaches, i.e., a six parameter Tait model and six parameter volume translations (temperature and pressure dependent) for Peng–Robinson and Patel–Teja EOS. The VS-PR model also represents well the isobaric thermal expansion and the isothermal compressibility coefficients of the pure cyclohexane, a small naphthenic substance as well as a long chain n-alkane hydrocarbon, n-hexadecane. When modeling the mixture data, the use of VS-PR model of pure components along with the Redlich–Kister expansion, truncated at the first term, the density was correlated within a RMSD only 60% greater than the experimental error. The proposed model is able to accurately represent all the tested mixture data with a relatively small number of parameters.     

Linear scaling local correlation approach for solving the coupled cluster equations of large systems

A linear scaling local correlation approach is proposed for approximately solving the coupled cluster doubles (CCD) equations of large systems in a basis of orthogonal localized molecular orbitals (LMOs). By restricting double excitations from spatially close occupied LMOs into their associated virtual LMOs, the number of significant excitation amplitudes scales only linearly with molecular size in large molecules. Significant amplitudes are obtained to a very good approximation by solving the CCD equations of various subsystems, each of which is made up of a cluster associated with the orbital indices of a subset of significant amplitudes and the local environmental domain of the cluster. The combined effect of these two approximations leads to a linear scaling algorithm for large systems. By using typical thresholds, which are designed to target an energy accuracy, our numerical calculations for a wide range of molecules using the 6-31G or 6-31G* basis set demonstrate that the present local correlation approach recovers more than 98.5% of the conventional CCD correlation energy.     

Geometries and properties of bimetallic phosphido-bridged complex Cp(CO)2W(μ-PPh2)W(CO)5 and Cp(CO)3W(μ-PPh2)W(CO)5

Complete geometry optimizations were carried out by HF and DFT methods to study the molecular structure of binuclear transition-metal compounds (Cp(CO)₃W(μ-PPh₂)W(CO)₅) (I) and (Cp(CO)₂W(μ-PPh₂)W(CO)₅) (II). A comparison of the experimental data and calculated structural parameters demonstrates that the most accurate geometry parameters are predicted by the MPW1PW91/LANL2DZ among the three DFT methods. Topological properties of molecular charge distributions were analyzed with the theory of atoms in molecules. (3, −1) critical points, namely bond critical point, were found between the two tungsten atoms, and between W1 and C10 in complex II, which confirms the existence of the metal–metal bond and a semi-bridging CO between the two tungsten atoms. The result provided a theoretical guidance of detailed study on the binuclear phosphido-bridged complex containing transition metal–metal bond, which could be useful in the further study of the heterobimetallic phosphido-bridged complexes.     

Elucidating Factors Manipulated the Formation of Multiply Charged Protein Homomultimeric Complexes by Electrospray Ionization

Native non‐covalently bonded protein‐protein and protein‐substrate complexes are of great interest and have been extensively studied by electrospray ionization mass spectrometry (ESI‐MS). Multiply charged protein homomultimeric complexes are shown to form by ESI‐MS. This study addresses factors that can artificially induce the formation of multiply charged protein homomultimeric complexes. Cytochrome c (Cyt c) and ubiquitin, which are monomers in solution, were found to generate (Cyt c)_mⁿ⁺ by electrospray ionization (ESI). The homomultimeric complexes were not limited to dimeric complexes but include also multiply charged trimers, tetramers, and pentamers. The observation of these homomultimeric complexes has never been revealed from a Cyt c solution at the concentration as low as 10 μM. Increasing the concentration of Cyt c enhanced the formation of (Cyt c)_mⁿ⁺ as expected; however, the protein concentration does not affect the relative intensities of monomeric and dimeric complexes. Additionally the enrichment of NH₄OH also promotes the formation of (Cyt c)_mⁿ⁺. Notably, source collision‐induced dissociations (source‐CID) of (Cyt c)_mⁿ⁺ alter the charge state distribution (CSD) and may lead to an incorrect interpretation of Cyt c conformations. Hence, extra care should be taken when using CSD to interpret the conformation of a protein derived from ESI‐MS.     

Laser field induced charge transfer: Para-nitroaniline coupled to a quantum mechanical radiation field

Summary We present a preliminary model for describing a solvated intramolecular charge transfer reaction coupled to a quantum mechanical radiation field. Actual calculations of energies and couplings were performed with a recently developed self-consistent reaction field response method. The representation of dressed molecular states is used for calculating state populations for various laser fields. The state populations are sensitive to the properties of the laser field.     

碘掺杂的3-乙基-5-[2-(3-乙基-2苯并噻唑啉基)亚乙基]罗丹宁的结构与电性能

The merocyanine dye 3-ethyl-5-(2-(3-ethyl-2-benzothiazolinylidene)-ethylidene)-rhodanine (BTER) known as Agfa-10 has been found to have a good photoconductivity as solution cast film. In this paper iodine-doped BTER was obtained by doping with iodine vapor. Its structure was investigated with the following characteristies. 1 The doped iodine had been excited as I_3~- anion. 2 Because the electron located on the sulphur atom was transferred to iodine, the charge transfer complex of (BTER-I_3) formed. 3 During the iodine doping process, BTER changed from α-form to β-modification. These had been identified by X-ray diffraction, VIS-absorption spectra and SEM picture.4 From the volt-Ampere curve obtained from sandwich cell, when E≤2.2×10~(-1) V·cm~(-1), the room temperature electrical conductivity of BTER and BTER-I_3 were found to be 2.22×10~(-10) s·cm~(-1) and 2.6×10~(-7) S·cm~(-1), respectively.     

Does ionized diacetylene have a positive proton affinity?

Singly and doubly charged C₄H₃^+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C₄H₃²⁺ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IE_v(C₄H₃⁺)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IE_a(C₄H₃⁺)=16.33 eV and IE_v(C₄H₃⁺)=16.49 eV for the most stable isomer H₂C=C---CCH⁺. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C₄H₂⁺ has indeed a positive proton affinity of PA(C₄H₂⁺)=1.50±0.42 eV.     

N-取代吩噻嗪和DDQ的电荷转移络合作用

具有盼嘤酸化学结构的化合物有广泛的用途I‘－＼其中吩嘤埃衍生物在医学上用作抗精神病药物特别受到药理学家们的注意，发现其药理作用与其分子提供电子的能力有关卜‘」但是我们应该注意到，作为抗精神病药物的吩嚷嚷衍生物，其吩座爆分子的氮原子都连有一个叔胺基链问，例如氯丙障（I）和奋乃静（11）．而我们知道，胺类特别是叔胺类有强的提供电子的能力＊；在上述的药物分子中是主要的提供电子因素，因此以这类化合物作为给体研究其供电子能力，是不能实际反映吩嘤嗓分子本身的给电子能力的．吩嘤噪类属于二苯并杂环化合物，分子中既…     

含氮给体结构对丙烯腈电荷转移光聚合的影响

<正> 对于正性烯类单体,主要是乙烯基咔唑的电荷转移聚合,诚田已作过详细综述。负性烯类单体的电荷转移聚合主要研究的单体是丙烯腈(AN)及甲基丙烯酸甲酯(MMA)。Barton等研究了芳烃为引发剂的MMA光聚合。我们研究了芳胺为引发剂的光聚合。 芳胺,尤其是芳叔胺,是较强的电子给体,与负性单体在光照下经激基复合物而引发聚合,我们的实验表明,吡啶及其同系物(喹啉与吖啶)并不象吡咯及其同系物(吲哚与咔唑)那样有效地引发AN等负性单体的光聚合(见表1)。从图1所示的结构看,它们有