共查询到20条相似文献,搜索用时 15 毫秒
1.
Takada T Kawai K Fujitsuka M Majima T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(13):3835-3842
A kinetic study of the single-step hole transfer in DNA was performed by measuring time-resolved transient absorption. DNA molecules with various sequences were designed and conjugated with naphthalimide (NI) and phenothiazine (PTZ) to investigate the sequence and distance dependence of the single-step hole transfer between guanines (Gs). Hole injection into DNA was accomplished by excitation of the NI site with a 355 nm laser pulse, and the kinetics of the hole-transfer process were investigated by monitoring the transient absorption of the PTZ radical cation (PTZ.+). Kinetic analysis of the time profile of PTZ.+ based on the kinetic model showed that the distance dependence of the hole-transfer process was significantly influenced by the DNA sequence. Results of temperature- and isotope-effect experiments demonstrated that the activation energy increased as the number of bridge bases separating the Gs increased. This is because of the distance-dependent reorganization energy and contribution of the proton-transfer process to the hole transfer in DNA. 相似文献
2.
The solvent dependence of the 2-naphthyl(carbomethoxy)carbene (2) singlet-triplet energy gap has been examined by time-resolved infrared (TRIR) and computational methods. The ground state of 2 changes from the triplet state in hexane to the singlet state in acetonitrile. Preferential stabilization of the singlet carbene is the result of its increased dipole moment in polar solvents. Variable-temperature TRIR experiments provide measurements of the enthalpic and entropic differences between (1)2 and (3)2 and suggest that solvent and geometry effects on the entropy of singlet and triplet carbenes can offset differences arising from spin multiplicity. B3LYP calculations using the polarizable continuum solvation model (PCM) reproduce the general trends in enthalpic differences seen experimentally. 相似文献
3.
4.
《Polyhedron》2005,24(16-17):2522-2527
Biradicaloid character of three Kekulé aromatic compounds containing two phenalenyl moieties is discussed on the basis of the theoretical and experimental results. DFT calculation of the compounds reveals a small HOMO–LUMO gap with a large spatial overlap between them, leading to a singlet biradical character in a ground state and an excited triplet biradical state with a small ΔES–T. Singlet biradical character for 1 (see Fig. 1) is indicated by the X-ray crystallographic analysis, which shows dimeric pairs with substantially short non-bonding contacts of ∼3.1 Å. The ESR measurements for 1 and 3 give typical spectra for triplet species and the temperature dependence of the half-field signal indicates the thermal excitation to the triplet states. 相似文献
5.
The charge recombination (CR) dynamics of geminate ion pairs formed by excitation of the ground-state donor-acceptor complexes in polar solvent have been investigated within the framework of stochastic approach. It is shown that for low exergonic reactions these dynamics critically depend on the reorganization energy of intramolecular high-frequency mode. Even moderate reorganization energies (0.1-0.2 eV) significantly accelerate the excited-state population decay making it nearly exponential. In the solvent-controlled regime, the majority of the excited donor-acceptor complexes recombine at nonthermal (hot) stage when the nonequilibrium initial wave packet passes through a number of term crossings corresponding to the transitions with creation of several vibrational quanta. Analysis of this mechanism allows to conclude (i) the CR in viscous solvents proceeds much faster than the diffusive relaxation of solvent, (ii) under certain conditions, the CR rate becomes practically independent of the diffusive component of solvent relaxation which is determined by solvent viscosity, (iii) in contrast to predictions of Marcus theory, the CR rate decreases monotonically with the rise of reaction exergonicity even at small free energy gaps, in accordance with experimental results. Two semiquantitative approaches providing rather simple analytical expressions for the hot charge recombination dynamics are suggested. These approximations give a good reproduction of the excited-state decay in the wide area of model parameters. 相似文献
6.
We have investigated the dependence of the electronic factor in electron-transfer rate constants on the energy gap and temperature by minimizing the electronic energy with respect to the instantaneous non-equilibrium solvent polarization. The electronic charge billows out and shrinks in the “normal” and strongly exothermic free energy region, respectively, but the effect is only comparable to the variation of the nuclear factor for low temperatures and strongly exothermic processes. 相似文献
7.
Adelio R. Matamala Alejandro A. Alarcón 《International journal of quantum chemistry》2012,112(5):1316-1322
A simple model for the calculation of HOMO and LUMO energy levels of benzocatafusenes (i.e., molecules that are only constituted by mutually condensed benzene rings and without interior carbon atoms, which belong to three benzene rings) is presented. Using semiempirical AM1 method, 615 benzocatafusenes were studied (29 normal and 586 branched). The relation between energy and molecular structure was coded by the three Hückel parameters: Coulomb integral, bond integral, and secular x eigenvalue. Analytical functions for HOMO and LUMO energy levels in terms of x parameter were obtained for normal benzocatafusenes, and energies for branched benzocatafusenes were satisfactorily modelled by the introduction of a simple correction function into the analytical functions describing normal benzocatafusenes. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012 相似文献
8.
1H NMR chemical shifts of antiaromatic species reveal an enhanced paratropic displacement. The high-field shifts exhibited by doubly charged benzenoid polycycles were shown to be strongly related to the LUMO-HOMO energy gaps in these antiaromatic systems. As the gap decreases, a larger paratropic shift was observed. 相似文献
9.
Yoshida N Ishizuka T Yofu K Murakami M Miyasaki H Okada T Nagata Y Itaya A Cho HS Kim D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2854-2866
A series of zinc(II) porphyrin-imide dyads (ZP-Im), in which an electron donating ZP moiety is directly connected to an electron accepting imide moiety in the meso position, have been prepared for the examination of energy gap dependence of intramolecular electron transfer reactions with large electronic coupling. The nearly perpendicular conformation of the imide moiety towards the porphyrin plane has been revealed by Xray crystal structures. The energy gap for charge separation, 1ZP* - Im --> ZP+ - Im-, is varied by changing the electron accepting imide moiety to cover a range of about 0.8 eV in DMF. Definitive evidence for electron transfer has been obtained in three solvents (toluene, THF, and DMF) through picosecond-femtosecond transient absorption studies, which have allowed us to determine the rates of photoinduced charge separation, 1ZP* - Im --> ZP+ - Im-, and subsequent thermal charge recombination ZP+ - Im- --> ZP - Im. The free-energy gap dependence (energy gap law) has been probed from the normal to the nearly top region for the charge separation rate alone, and only the inverted region for the charge recombination rate. Although both of the energy gap dependencies can be approximately reproduced by means of the simplified semiclassical equation, when we take into consideration the effect of the high frequency vibrations replaced by one mode of averaged frequency, many features, including the effects of solvent polarity and the electron tunneling matrix element on the energy gap law, differ considerably from those of the previously studied porphyrin-quinone systems, which have weaker interchromophore electronic interactions. 相似文献
10.
Li Xiaojun Ma Ruijie Liu Tao Xiao Yiqun Chai Gaoda Lu Xinhui Yan He Li Yongfang 《中国科学:化学(英文版)》2020,63(9):1256-1261
To achieve high-efficiency polymer solar cells(PSCs), it is not only important to develop high-performance small molecule acceptors(SMAs) but also to find a matching polymer donor to achieve optimal morphology and matching electronic properties.Currently, state-of-the-art SMAs mostly rely on a donor polymer named PM6. However, as the family of SMAs continues to expend, PM6 may not be the perfect polymer donor due to the requirement of energy level matching. In this work, we tune the energy level of PM6 via the strategy of ternary copolymerization. We achieve two donor polymers(named PL-1 and PL-2) with upshifted HOMO(the highest occupied molecular orbital) energy level(compared with PM6), and can thus match with the SMAs with upshifted HOMO energy levels compared with Y6. These two copolymers exhibit slightly higher order of molecular packing and similar charge transport properties, which demonstrate that the method of ternary copolymerization can fine tune the HOMO level of donor polymers, while the morphology and mobility of the blend film remain mostly unaffected. Among them,the best device based on PL-1:Y6 exhibits power conversion efficiencies(PCEs) of 16.37% with lower open circuit voltage(Voc)but higher short circuit current voltage(Jsc) and fill factor(FF) than that of the device based on PM6:Y6. This work provides an effective approach to find polymer matches for the SMAs with upshifted HOMO levels. 相似文献
11.
A new series of oligomers consisting of thiophene as p-type unit and oxadiazole as n-type unit were synthesized, and their photophysical and electrochemical properties were evaluated. Cyclic voltammography studies demonstrated that the electronic properties of the p-n diblock oligomers could be modulated by changing the number of thiophene and oxadiazole rings. The molecular regiochemical effect to the electrochemical and optical properties was also investigated. 相似文献
12.
Wan JH Feng JC Wen GA Wei W Fan QL Wang CM Wang HY Zhu R Yuan XD Huang CH Huang W 《The Journal of organic chemistry》2006,71(7):2565-2571
A novel series of oligomers consisting of thiophene as a p-type unit and oxadiazole as an n-type unit were separately synthesized. On the basis of the characterization of photophysical and electrochemical properties, the structure-property relationships of the oligomers were investigated. Cyclic voltammogram studies showed that changing the number of thiophene and oxadiazole units could effectively modulate the electronic properties of the p-n diblock and triblock oligomers. The effect of molecular regiochemistry on electronic properties is also investigated. The observed electronic properties were consistent with theoretical calculations. These systems serve as excellent examples, demonstrating the band gap control principle in the p-n heterostructure oligomers. 相似文献
13.
Tuning the HOMO and LUMO energy levels of organic chromophores for dye sensitized solar cells 总被引:1,自引:0,他引:1
Hagberg DP Marinado T Karlsson KM Nonomura K Qin P Boschloo G Brinck T Hagfeldt A Sun L 《The Journal of organic chemistry》2007,72(25):9550-9556
A series of organic chromophores have been synthesized in order to approach optimal energy level composition in the TiO2-dye-iodide/triiodide system in the dye-sensitized solar cells. HOMO and LUMO energy level tuning is achieved by varying the conjugation between the triphenylamine donor and the cyanoacetic acid acceptor. This is supported by spectral and electrochemical experiments and TDDFT calculations. These results show that energetic tuning of the chromophores was successful and fulfilled the thermodynamic criteria for dye-sensitized solar cells, electrical losses depending on the size and orientation of the chromophores were observed. 相似文献
14.
快速简便测定有机电致发光材料HOMO能级的电化学方法 总被引:3,自引:0,他引:3
采用多层结构有利于提高有机电致发光 (or ganicelectroluminescence ,OEL)器件的效率和寿命[1 3] 。为了有依据地选择多层有机材料 ,就要准确表征其能带。表征有机材料能带的一些方法有的因为得不到理想结果、有的因为仪器昂贵未被普遍采用[4] 。而用电化学方法 (如循环伏安法 )表征有机材料的能带所用仪器设备简单 ,操作方便 ,被广泛使用。常用OEL器件中所选用有机物的氧化、还原电位较大 ,体系中的少量杂质 (如水、氧气等 )的电化学活性就会表现出来。因此 ,须保证体系在测定时水、氧气的含量足够低。… 相似文献
15.
The relationship between the calculated energy of the HOMO-LUMO gap, where (epsilonLUMO - epsilonHOMO)/2 is defined as DeltaHL, and of the longest wavelength transition in the UV-visible spectrum, DeltaE, was examined for a series of aromatic and antiaromatic cations and dications. TD-DFT calculations accurately modeled the energies of a series of dications including fluorenylidene dications whose UV-visible spectra are reported, as well as the energies of a series of aromatic and antiaromatic monocations whose spectra were previously reported. There is a linear correlation of the energy of the longest wavelength transition, DeltaEcalc, with DeltaHL. There is no linear relationship between DeltaEcalc and the sum of the NICS values, but there is a linear relationship between DeltaEcalc multiplied by the number of atoms in the conjugated system, DeltaEcalcT, and the sum of the NICS values. There is also an approximate linear relationship between the average 1H NMR shift and the sum of the NICS values. These relationships give further support to the suggestion that the magnetic and energetic criteria of aromaticity and antiaromaticity are related. Furthermore, the data suggest that species that have DeltaEcalcT < 20 are antiaromatic whereas those with DeltaEcalcT > 30 are aromatic. 相似文献
16.
Fifteen C36 isomers were examined to determine the influence that the quality of basis sets has on the geometry parameters, the relative stability and HOMO–LUMO energy gaps of fullerene isomers calculated with density functional theory. It is worthwhile to note that the geometry parameters of all C36 isomers are insensitive to basis sets. On the other hand, one set of d-type polarization functions plays an important role in evaluating relative stability and HOMO–LUMO energy gaps, while diffuse functions are not effective. To obtain reliable energies, at least a double-zeta plus polarization basis set is required, and a triple-zeta plus polarization basis set is suggested to lead to accurate energies at a reasonable computational cost. 相似文献
17.
John Haseltine 《Tetrahedron letters》2010,51(25):3280-3283
To better understand acyl transfer reactions of oligopeptides, seventeen N-acyl amino acid esters were solvolyzed in mildly basic methanol-d4. All show pseudo-first-order kinetics by 1H NMR. The rate constant varies up to 400-fold with the identity of the amino acid and up to 6200-fold with the identity of the N-acyl group. The impact of the N-acyl group on the rate constant is discussed in terms of crowding, amide conformation, and amide CO bond character. 相似文献
18.
Pedatsur Neta Yamil Simon-Manso Xiaoyu Yang Stephen E. Stein 《Journal of the American Society for Mass Spectrometry》2009,20(3):469-476
The energy dependence of fragmentation in a collision cell was measured for 2400 protonated peptide ions derived from the
digestion of 24 proteins. The collision voltage at which the sum of the fragment ion abundances was equal to the remaining
parent ion (V
1/2) was the principal measure of fragmentation effectiveness. Each class of peptides was characterized by a linear relation
between V
1/2 and m/z whose slope depended on the peptide class and, with little adjustment, intersected the origin. Peptide ions where the number
of protons is no greater than the number of arginine residues show the greatest slope, V
1/2/(m/z)=0.0472 (all slopes in units of V Da−1 e). For peptides where the number of protons is greater than the number of arginines, but not greater than the total number
of basic residues, the slope decreases to 0.0414 for singly charged ions, 0.0382 for doubly charged, 0.0346 for triply charged,
and 0.0308 for more highly charged ions. With one mobile proton, the slope is about 0.029 for singly and doubly charged ions
and slightly lower for more highly charged ions. With two or more mobile protons the slope is 0.0207. By removing m/z dependence, the deviation of V
1/2 from a line provides a relative measure of the ease of fragmentation of an ion in each class. This information can guide
the selection of optimal conditions for tandem mass spectrometry studies in collision cells for selected peptide ions as well
as aid in comparing the reactivity of ions differing in m/z and charge state. 相似文献
19.
The Casimir–Polder retarded dispersion energy is calculated for non-symmetric molecules and the energy is expressed in terms of body fixed axes for the dipole transition moments on each molecule. In the special case of molecules with cylindrical symmetry the potential energy is given in terms of the transverse and longitudinal polarizabilities and in terms of the angles defining the orientation of the axes of the molecules with respect to the intermolecular direction. In the limit of no retardation (R ? λ) the result becomes that of London and in the opposite limit of full retardation at large R the potential energy tends to that of Craig and Power. 相似文献
20.
The energy relaxation of the lowest vibrational level (υ = 1) of liquid oxygen in the electronic ground state was investigated within a wide temperature range (53.4 K ? T ? 96 K). The relaxation time exhibits a peak value of τ′ ≈ 3.1 ms around 65 K and is shorter at lower and higher temperatures. The observed temperature behavior is discussed in view of theoretical models of energy relaxation in liquids. 相似文献