共轭高分子链中电荷迁移的热效应

从理论上研究了共轭高聚物链中在电场作用下极化子运动的热效应.基于SSH模型以及通过绝热动力学演化的方法,模拟了共轭高聚物链中极化子在电场作用下从链左端向右端运动的过程.晶格受到的热扰动作用假设为通过局域的晶格范围内原子位移的随机涨落来实现.结果发现,晶格中的局域热涨落对于运动中的极化子而言等效于一个势垒.势垒高度由高分子中受到热扰动的区域的范围大小以及该区域与其周围环境的温差来决定.当分子中存在热吸收不均匀的现象时,链内极化子迁移率在低电场范围内随电场的变化遵循对数曲线变化规律.     

Precursor states for charge carrier generation in conjugated polymers probed by ultrafast spectroscopy

Photocurrent experiments using two femtosecond laser pulses are performed on a photodiode using a ladder-type conjugated polymer as the active layer. With a photon energy of 3.1 eV the first pulse excites singlet excitons. A time-delayed second pulse with a photon energy of 2.49 eV leads to a decrease of the photocurrent by exciton depletion due to stimulated emission. S1 excitons being dissociated during their entire lifetime are identified as the only relevant channel for charge carrier generation. Intrachain polaron pairs are also formed on an ultrafast time scale with a yield of approximately 10%. They can be efficiently dissociated by reexcitation with photons of an energy of 1.9 eV.     

Stark spectroscopy of excited-state transitions in a conjugated polymer

Stark spectroscopy, which is well established for probing transitions between the ground and excited states of many material classes, is extended to transitions between transient excited states. To this end, it is combined with femtosecond pump-probe spectroscopy on a conjugated polymer with appropriately introduced traps which harvest excitation energy and build up a sufficient excited state population. The results indicate a significant difference in the effective dipole moments between two short lived excited states.     

Direct visualization of the charge transfer in conjugated polymers

Ion-induced charge-transfer states in conjugated polyelectrolytes were experimentally investigated by Justin M.Hodgkiss and his co-workers [J Am Chem Soc,2009,131(25):8913].In this work,charged and neutral conjugated polyelectrolytes were further studied with quantum chemistry methods.The calculation result shows that the absorption spectra are roughly in visible and ultraviolet light regions,and the two absorption peaks are located in the wavelength span 300-400 nm for charged polyelectrolytes.However,in n...     

Role of mesoscopic morphology in charge transport of doped polyaniline

In doped polyaniline (PANI), the charge transport properties are determined by mesoscopic morphology, which in turn is controlled by the molecular recognition interactions among polymer chain, dopant and solvent, Molecular recognition plays a significant role in chain conformation and charge delocalization. The resistivity of PANI doped by camphor sulfonic acid (CSA)/2-acrylo-amido-1-propane sulfonic acid (AMPSA)/dodecyl benzene sulfonic acid (DBSA) is around 0.02 Ω cm. PANI-CSA and PANI-AMPSA show a metallic positive temperature coefficient of resistivity above 150 K. with a finite value of conductivity at 1.4 K; whereas, PANI-DBSA shows hopping transport at low temperatures. The magnetoresistance is positive (negative) for PANI-CSA (PANI-AMPSA); and PANI-DBSA has a large positive MR. The behavior of MR suggests subtle variations in mesoscopic morphology between PANI-CSA and PANI-AMPSA.     

Nonequilibrium mesoscopic transport: a genealogy

Models of nonequilibrium quantum transport underpin all modern electronic devices, from the largest scales to the smallest. Past simplifications such as coarse graining and bulk self-averaging served well to understand electronic materials. Such particular notions become inapplicable at mesoscopic dimensions, edging towards the truly quantum regime. Nevertheless a unifying thread continues to run through transport physics, animating the design of small-scale electronic technology: microscopic conservation and nonequilibrium dissipation. These fundamentals are inherent in quantum transport and gain even greater and more explicit experimental meaning in the passage to atomic-sized devices. We review their genesis, their theoretical context, and their governing role in the electronic response of meso- and nanoscopic systems.     

Spectroscopic studies on conjugated polymers in mesoporous channels: influence of polymer side-chain length

The influence of mesoporous environment on the conjugated polymers was studied by UV-Vis absorption and Photoluminescence spectroscopy. The applied polymers were three novel poly(p-phenylenevinylene) derivatives (DDMA-PPV). These polymers have dibenzothiophen-5,5-dioxide units in their backbones, but are different from each other in the length of alkoxy side-chains. The polymers were incorporated into the mesoporous channels of SBA-15 by sorption from their dilute solutions. The confined polymers exhibited different trends in the shifts of the absorption onsets and the emission peaks depending on the length of the side-chains. The polymer with shorter side-chain showed red-shifts in both the absorption and emission spectra, whereas the polymer with longer side-chain showed blue-shifts. These phenomena were caused by the combined influences from the electronic confinement and the conformation distortion. Moreover, these trends were enhanced when the polymers were loaded in amine-modified SBA-15.     

Semiconductor nanocrystals in carrier-transporting polymers: Charge generation and charge transport

By incorporating semiconductor nanocrystals in carrier-transporting polymers, an interesting class of photoconductive nanocomposites is created. The presence of semiconductor nanocrystals enhances the photoinduced charge generation efficiency and extends the sensitivity range, while the polymer matrix is responsible for charge transport. A wide variety of semiconductors and polymers have been used. In this paper, we review material synthesis and discuss the effects of semiconductor nanocrystals on the charge transport and charge generation properties.     

共轭聚合物中链内无序效应对极化子输运的影响

基于扩展的Su-Schrieffer-Heeger紧束缚模型, 利用非绝热动力学方法研究了链内无序效应对共轭聚合物中极化子输运机制的影响. 研究发现, 极化子的输运由外加电场和链内无序效应共同作用的结果所决定. 在一般情况下, 链内无序效应不利于极化子的输运, 但随着电场强度的增大, 无序对极化子输运的影响减小. 关键词： 共轭聚合物 极化子输运 链内无序     

Time-resolved charge carrier generation from higher lying excited states in conjugated polymers

Sub-ps three-pulse transient differential transmission spectroscopy using two excitation pulses is used to directly investigate the generation of charge carriers in ladder-type poly(para)phenyl in bulk film. The role of higher excited singlet states of both even and odd symmetry is examined and the dynamics of the major processes involved is described quantitatively. The charge generation efficiency is found to depend strongly on the delay between the two excitation pulses. This is explained by the interplay between internal conversion, excitation energy migration, and on-site vibronic relaxation.     

Exact analytical results on electronic transport of conjugated polymer junctions: Renormalization method

We study the electrical coherent transport in a typical conjugated polymer connected to molecular electrodes. We provide an exact analytical method to reduce such a system to a uniform wire by employing Green’s function theory and the tight-binding Hamiltonian. The formalism is useful to investigate transport properties of periodic quasi-one dimensional molecular nanowires and polymers in the presence or absence of defects. Some illustrative examples including polyacetylene and poly(p-phenylene) polymers are given to show the ability of our approach. For ideal infinite polyacetylene and poly(p-phenylene) polymers due to dimerization respectively, one and two gaps will appear in the density of states spectra.     

Singlet-triplet transition in a quantum dot: effect on mesoscopic transport

The T=0 transport properties of a wire interacting with a lateral two-level quantum dot are studied by using an exact numerical calculation. The wire conductance, the spin–spin correlation and the Kondo temperature are obtained as a function of the dot level energy spacing. When the dot has two electrons and spin S_D1, the wire current is totally quenched by the S=1 Kondo effect. The Kondo temperature is maximum at the singlet–triplet transition and its dependence upon the dot energy spacing follows a non-universal scaling law.     

Charge transport in low-concentration MEH-PPV conjugated polymer/fullerene composites

Charge transport was studied in composites of poly[2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylene-vinylene] (MEH-PPV) conjugate polymer and low-concentration fullerenes (C₆₀) below the percolation threshold. The electron mobility showed a linear increase with the fullerene concentration, to which the hole mobility was insensitive. Our results indicate that fullerene–polymer networks provide a conduction path to the electrons, whereas the holes are transported through the polymer-only paths. The microscopic environments of the two distinct conduction paths in the composites as revealed by the electric field dependence of the mobilities are also discussed.     

共轭高分子链中极化子间相互作用对电荷迁移率的影响

基于综合考虑了电子与声子以及电子与电子相互作用的理论模型,采用数值方法计算了在外电场作用下共轭高聚物分子中电荷的迁移率,讨论了大小极化子共存并相互作用对分子链内电荷迁移率的影响。研究发现,电荷迁移率明显受大小极化子的载荷性质的影响,当大小极化子具有相同电性时,在低电场范围内,分子内电荷迁移率由大极化子运动性质主导,而在高电场范围内,分子内电荷迁移率由小极化子主导;另一方面,当大小极化子具有相反电性时,电荷迁移率只由大极化子运动性质主导,与电场强度无关。此外,还讨论了电子与电子相互作用对电荷迁移率"的影响。     

Photoinduced charge currents in mesoscopic rings

The temporal and spatial controllability of charge distribution in submicron structures opens new avenues for potential applications and for the understanding of nonequilibrium processes. Here we suggest a novel way to trigger and control within picoseconds charge currents and magnetic moments in nanoscopic and mesoscopic ring structures by applying two shaped, time-delayed light pulses. Our quantum dynamic calculations show that the magnitude and direction of the induced currents are tunable by varying the time delay and strengths of the pulses. Furthermore, in an array of rings desirable magnetic orders are generated depending on the ring sizes and particle number.     

Simultaneous Raman and fluorescence spectroscopy of single conjugated polymer chains

Simultaneous surface enhanced Raman scattering (SERS) and fluorescence is demonstrated from single conjugated polymer chains. As resonance enhancement of SERS depends on the spectral overlap of the polymer's absorption and the incident laser, resonance Raman and fluorescence effectively probe the absorbing and emitting part of the polymer, respectively. The optical phonon energies change along the polymer chain, providing a window to spatially track excited state relaxation. Whereas a mean spatial redistribution of the excitation is witnessed by a change in vibronic fingerprint following interchromophoric energy transfer, intrachromophoric exciton self-trapping leaves the vibrations unchanged.     

Infrared diode laser and millimeter-wave spectroscopy of the NCl radical: Vibrational and isotopic dependences of molecular constants

The infrared diode laser and millimeter-wave spectra of the nitrogen chloride radical in the X³Σ⁻ state have been observed in a DC glow discharge plasma of a N₂ and Cl₂ mixture, yielding spectroscopic information on ¹⁴N³⁵Cl up to v = 4 and ¹⁴N³⁷Cl up to v = 3. The observed infrared and millimeter-wave spectra have been simultaneously included in a least-squares analysis to determine Dunham coefficients for the vibrational and rotational energies and similar terms for the fine structure interactions. The analysis has shown that isotopic relations based on the Born-Oppenheimer approximation do not hold for the vibrational frequency, the rotational constant, and the spin-spin and spin-rotation interaction constants. It has been found that the first derivative of the spin-spin interaction constant with respect to the internuclear distance is correlated with the change in the equilibrium internuclear distance caused by the b¹Σ⁺ ← X³Σ⁻ excitation.