Vibrational control of molecular electron transfer reactions

ABSTRACT

Vibrational motions promote molecular electron transfer (ET) reactions by bringing electron donor and electron acceptor electronic states to fleeting resonance, and by modulating the donor-to-acceptor electronic coupling. The main experimental signature of molecular motion effects on the ET rate is the temperature dependence of the rate, which gives information about the overall free energy activation barrier for the ET reaction. Another approach to probing the vibrational control of ET reactions is to excite specific electron-transfer-active vibrational motions by external infrared (IR) fields. This type of experimental probe is potentially more specific than thermal excitation and recent experiments have shown that molecular ET rates can be perturbed by mode-specific IR driving. We review the theory and experiments of vibrational control of ET rates, and discuss future challenges that need to be tackled in order to achieve the mode-specific tuning of rates.     

Coherent-phonon-assisted excitation transfer via optical near fields in dilute magnetic semiconductor nanostructures

Optical near-field (ONF) phenomena observed in nanoscale systems have been applied to nano-fabrication and nano-photoelectronic devices for the last decade. Excitation transfer (ET) is an elementary process caused by ONF interaction localized at the nanoscale in real space. Recently, we have observed spin-dependent ET controlled by an external field and discovered the sign of assistance of phonons. In this work, we elucidate that the assistance of coherent phonons in ET originates from two types of mechanism: energy resonance between exciton levels renormalized by phonon effects and enhancement by phase matching between coherent oscillation of populations and phonon oscillation. This study will stimulate the development of the application of ET via a ONF to nano-photoelectronic devices.     

Quantum Transport through a Triple Quantum Dot System in the Presence of Majorana Bound States

We study the electron transport through a special quantum-dot(QD)structure composed of three QDs and two Majorana bound states(MBSs)using the nonequilibrium Green’s function technique.This QD-MBS ring structure includes two channels with the two coupled MBSs being Channel 1 and one QD being Channel 2,and three types of transport processes such as the electron transmission(ET),the Andreev reflection(AR),and the crossed Andreev reflection(CAR).By comparing the ET,AR,and CAR processes through Channels 1 and 2,we make a systematic study on the transport properties of the QD-MBS ring.It is shown that there appear two kinds of characteristic transport patterns for Channels 1 and 2,as well as the interplay between the two patterns.Of particular interest is that there exists an AR-assisted ET process in Channel 2,which is different from that in Channel 1.Thus a clear"X"pattern due to the ET and AR processes appears in the ET,AR,and CAR transmission coefficients.Moreover,we study how Channel 2 affects the three transport processes when Channel 1 is tuned in the ET and CAR regimes.It is shown that the transport properties of the ET,AR and CAR processes can be adjusted by tuning the energy level of the QD embedded in Channel 2.We believe this research should be a helpful reference for understanding the transport properties in the QD-MBS coupled systems.     

Femtosecond time-resolved energy transfer from CdSe nanoparticles to phthalocyanines

The first real-time observation of the early events during energy transfer from a photoexcited CdSe nanoparticle to an attached phthalocyanine molecule are presented in terms of a femtosecond spectroscopic pump–probe study of the energy transfer in conjugates of CdSe nanoparticles (NPs) and silicon phthalocyanines (Pcs) with 120 fs time resolution. Four different silicon phthalocyanines have been conjugated to CdSe NPs. All of these have proven potential for photodynamic therapy (PDT). In such NP-Pc conjugates efficient energy transfer (ET) from CdSe NPs to Pcs occurs upon selective photoexcitation of the NP moiety. Spectral analysis as well as time-resolved fluorescence up-conversion measurements revealed the structure and dynamics of the investigated conjugates. Femtosecond transient differential absorption (TDA) spectroscopy was used for the investigation of the non-radiative carrier and ET dynamics. The formation of excitons, trapped carriers states, as well as stimulated emission was monitored in the TDA spectra and the corresponding lifetimes of these states were recorded. The time component for energy transfer was found to be between 15 and 35 ps. The ET efficiencies are found to be 20-70% for the four Pc conjugates, according to fluorescence quenching experiments. Moreover, as a result of the conjugation between NP and the Pcs the photoluminescence efficiency of the Pc moieties in the conjugates do not strictly follow the quantum yields of the bare phthalocyanines. PACS 73.63.Bd     

铝氢化物(AlHn)(n=1-6)团簇结构与光谱的研究

采用密度泛函(DFT)中的B3P86方法,在Dunning的相关一致基组cc-PVTZ水平上,对铝氢化物(AlHn)(n=1-6)团簇的可能几何构型进行优化计算,得出最稳定构型的几何参数、电子结构、振动频率和光谱等性质参数,并给出了最稳定结构的总能量(ET)、结合能(EBT)、平均结合能(Eav)、电离势(EIP)、能隙(Eg)、费米能级(EF)和氢原子差分吸附能(Ediff)等．结果表明铝氢化物团簇基态稳定结构的电子态分别为：n为奇数为单重态 和 ,n为偶数为双重态 和 ;由于Al原子属于缺电子原子,能与等电子原子H化合,通过氢桥键形成氢化物,本文优化计算发现,铝氢化物团簇最稳定的构型都存在氢桥键,且n为奇数的氢化物的氢桥键作用比相邻偶数的氢化物强．最后计算了铝氢化物团簇最稳定结构的红外光谱、平均结合能、电离势、能隙和费米能级等动力学电子特性,分析得出(AlHn)(n=1-6)团簇中AlH3的电离势和能隙最大,说明该氢化物最稳定,氢原子差分吸附能最大．     

铝氢化物(AlHn)(n=1-6)团簇结构与光谱的研究

采用密度泛函(DFT)中的B3P86方法，在Dunning的相关一致基组cc-PVTZ水平上，对铝氢化物(AlHn)(n=1-6)团簇的可能几何构型进行优化计算，得出最稳定构型的几何参数、电子结构、振动频率和光谱等性质参数，并给出了最稳定结构的总能量(ET)、结合能(EBT)、平均结合能(Eav)、电离势(EIP)、能隙(Eg)、费米能级(EF)和氢原子差分吸附能(Ediff)等．结果表明铝氢化物团簇基态稳定结构的电子态分别为：n为奇数为单重态 和 ，n为偶数为双重态 和 ；由于Al原子属于缺电子原子，能与等电子原子H化合，通过氢桥键形成氢化物，本文优化计算发现，铝氢化物团簇最稳定的构型都存在氢桥键，且n为奇数的氢化物的氢桥键作用比相邻偶数的氢化物强．最后计算了铝氢化物团簇最稳定结构的红外光谱、平均结合能、电离势、能隙和费米能级等动力学电子特性，分析得出(AlHn)(n=1-6)团簇中AlH3的电离势和能隙最大，说明该氢化物最稳定，氢原子差分吸附能最大．     

一类电子俘获型红外可激发材料光学性能研究

测试了硫化助熔剂法制备的电子俘获型红外可激发材料Ｅｕ，Ｓｍ∶ＣａＳ和Ｃｅ，Ｓｍ∶ＣａＳ的激发光谱、红外激励光谱、荧光光谱及红外上转换发光光谱等，结果表明：这类材料不仅具有红外上转换及光存储功能，而且具有光谱响应范围广、可在室温下工作以及造价低等优点，是一类很有发展前途的光学功能材料。     

Enhanced emission of 2.7 μm pumped by laser diode from Er3+/Pr(3+)-codoped germanate glasses

A novel Er(3+)/Pr(3+) codoped germanate glass was fabricated and analyzed. Efficient emission at 2.7 μm from the glass was observed upon excitation of a conventional 980 nm laser diode. The 2.7 μm emission characteristics and energy transfer (ET) were investigated. Population inversions between ?I(13/2) and ?I(11/2) levels have been achieved, and an enhanced emission from 2550 to 2800 nm was obtained. Large ET efficiency of 95% indicates that the ET process from Er(3+) to Pr(3+) (?I(13/2), 3H?)→(?I(15/2), 3F?) is efficient and that Pr(3+) can enhance the emission of 2.7 μm by quenching the lower laser level of Er(3+) via ET.     

Role of sugar in controlling reaction pathways: A study with thymine and thymidine

Magnetic field effect in conjunction with laser flash photolysis have been used for studying interactions of 9,10-anthraquinone and 2-methyl 1,4-naphthoquinone (menadione) with a DNA base, thymine (Thy) and its nucleoside, thymidine (dThd). Irrespective of medium Thy has been found to support both electron transfer (ET) and hydrogen abstraction with the quinones while dThd has exhibited a complete reluctance towards ET. This unique behavior of dThd has been attributed to a failure in attaining aromaticity by virtue of keto-enol tautomerism upon addition of a sugar moiety. Electron withdrawing effect of sugar unit is also considered responsible for reduction of ET from dThd. Again both Thy and dThd have exhibited hydrogen abstraction in homogeneous medium, which is normally unexpected. The above behaviors of the bases have been explained on the basis of their chemical structures.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Photoinduced energy transfer from the triplet state of naphthalene moiety in the Tb/Eu complexes of a specially designed naphthalene cryptand

The paper reports time-resolved emission and energy transfer (ET) studies of metal ion complexes of a specially designed rigid macrocyclic naphthalene cryptand (L) under different conditions. Complex formation of L with Li⁺ and H⁺ causes an appreciable increase in singlet state quantum yield and lifetime of L implying photoinduced electron transfer (PET) from the cryptand moiety to naphthalene unit in the free L. The system exhibits photoinduced ET at 77 K in its Tb³⁺ and Eu³⁺ complexes with either NO₃⁻¹ or Cl⁻¹ as counter-anion. The extent of ET is higher for the Tb³⁺ complex as compared to that for the Eu³⁺ complex. In both Tb³⁺ and Eu³⁺ complex, the NO₃⁻¹ ions influence the relative orientation of donor (L) and acceptor (Ln³⁺) more in favour of ET than the Cl⁻¹ ions. The rate constants for the ET from the naphthalene moiety of L to the acceptor (Ln³⁺) have been evaluated at 77 K. The results suggest ET from the triplet state of naphthalene using an exchange mechanism. The ground state geometries of the system L and its complexes with Li⁺, Cs⁺ and Tb³⁺ have been determined using DFT methods to interpret our results.     

Are there Efimov trimers in hexafluorobenzene rather than in benzene vapor itself?

Is there a spectroscopic method to detect an Efimov state? Following our proposal of an Efimov state arising from three pseudo bosons (generalized Cooper pairs) in benzene, our spectroscopic studies have found no evidence of Efimov trimers (ET) in h₆- or d₆-benzene. However, hexafluoro-benzene has shown peaks that we attributed to ET and the pseudo bosons. The experimental evidence suggests that benzene pseudo bosons and subsequently ET are quite sensitive to the surroundings.     

虚时间分裂算符方法研究溶剂电子转移动力学

在Sumi-Marcus理论中，采用虚时间分裂算符方法研究电子转移动力学．此方法具体应用于计算嗪-1和N,N-二甲基苯胺分子之间的电子转移速率常数．通过计算得到的两种反应物态的平均速率常数和一个长时间的速率常数，揭示了不同的sink函数时的电子转移动力学．在数值模拟过程中还发现了一些新的电子转移特性．     

Shift of the photoemission threshold in III–V and II–VI semiconductors

The reasons why the photoemission threshold energy of semiconductors is lower than the ionization energy of constituent atoms have been investigated. It has been indicated that the previously proposed interpretation of this phenomenon based on the inclusion of an additional intra-atomic Coulomb interaction between the valence electrons is insufficient. It has been shown that the calculation of the electronic energy structure of semiconductors, in particular, of the photoemission threshold, requires taking into account a change in the localization region of the valence electrons when a free atom is embedded into a crystal. A way of taking this change into account in the tight-binding theory has been demonstrated. Corrections to the tight-binding Hamiltonian have been found. The photoemission thresholds of III–V and II–VI semiconductors have been calculated with the inclusion of these corrections. Comparison of the results with the experimental data has been performed.     

Investigation of relaxation processes in nanocrystalline cobalt produced by severe plastic deformation

It has been shown that the dependence of the width of X-ray diffraction lines of plastically deformed cobalt on the annealing temperature is described by the exponential function. Characteristic temperature regions corresponding to the processes of recovery and recrystallization have been established. It has been shown that the values of the activation energy of recrystallization determined from the experimental data are comparable with the activation energy of the grain-boundary diffusion in metals. The activation energy for the recovery region is considerably lower than the activation energy of migration of nonequilibrium grain boundaries in nanocrystalline metals. The X-ray diffraction data have been confirmed by the investigations of the microstructure and microhardness.     

Low energy ion scattering by atomic steps on the single crystal surface

The energy, angular distributions and trajectories of particles scattered on surfaces of Ni(100) and Cu(100), with both ideal and damaged, and semi-infinite and isolated atomic steps, have been calculated. It has been shown that from the correlation between the experimental and calculated energy distributions of the scattered particles, one may determine the spatial extension of the isolated atomic steps and the distance between them on the single crystal surface damaged by ion bombardment. The energy and angular distributions of ions dechanneled from semi-infinite steps on the GaP(100) surface have been presented. It has been shown that the dechanneling ions form the characteristic peaks in the angular and energy distributions of the scattered particles.     

Comparative analysis of characteristic electron energy loss spectra and inelastic scattering cross-section spectra of Fe

The inelastic electron scattering cross section spectra of Fe have been calculated based on experimental spectra of characteristic reflection electron energy loss as dependences of the product of the inelastic mean free path by the differential inelastic electron scattering cross section on the electron energy loss. It has been shown that the inelastic electron scattering cross-section spectra have certain advantages over the electron energy loss spectra in the analysis of the interaction of electrons with substance. The peaks of energy loss in the spectra of characteristic electron energy loss and inelastic electron scattering cross sections have been determined from the integral and differential spectra. It has been shown that the energy of the bulk plasmon is practically independent of the energy of primary electrons in the characteristic electron energy loss spectra and monotonically increases with increasing energy of primary electrons in the inelastic electron scattering cross-section spectra. The variation in the maximum energy of the inelastic electron scattering cross-section spectra is caused by the redistribution of intensities over the peaks of losses due to various excitations. The inelastic electron scattering cross-section spectra have been analyzed using the decomposition of the spectra into peaks of the energy loss. This method has been used for the quantitative estimation of the contributions from different energy loss processes to the inelastic electron scattering cross-section spectra of Fe and for the determination of the nature of the energy loss peaks.     

Recovery of the metallic state and quantum oscillations in a dielectric salt of the (ET)8[Hg4X12(C6H5Y)2] family at X = Y = Br under compression

The quasi-two-dimensional organic conductor (ET)₈[Hg₄Br₁₂(C₆H₅Br)₂] (ET is bis(ethylenedithio)tetrathiafulvalene) undergoes a metal-insulator phase transition at T ∼ 170 K. It has been shown that a pressure of 8 kbar suppresses this transition and holds a metallic state to liquid-helium temperatures. Shubnikov—de Haas quantum oscillations with the single frequency F = 215 T have been observed in a magnetic field up to 15 T. The properties of this salt are compared to the properties of the (ET)₈[Hg₄Cl₁₂(C₆H₅Cl)₂] salt of the same family. Time annealing provides an important effect on the conducting properties of the salt under investigation. Original Russian Text ? R.B. Lyubovskii, S.I. Pesotskii, R.N. Lyubovskaya, E.I. Zhilyaeva, O.A. Bogdanova, 2009, published in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2009, Vol. 89, No. 11, pp. 685–687.     

On the theory of nonadiabatic bridge-mediated electron transfer

Effects of structural and energetic disorder on nonadiabatic electron transfer (ET) reactions are discussed theoretically. To account for the sequential as well as the superexchange mechanism of ET our recent approach is used presented in J. Phys. Chem. A 105, 10176 (2001). The overall charge motion is characterized by the numerical solution of rate equations for the electronic state populations and an averaging with respect to the disorder configurations. Introducing a single effective transfer rate which can be deduced from the experiment the dependence of this rate is discussed on the geometry of the ET system as well as on the disorder model. The theory is applied to donor-acceptor complexes connected by oligomers of the amino acid proline. In particular, a pronounced dependence is found of the effective transfer rate on disorder with respect to the reorganization energy.Received: 14 April 2003, Published online: 22 July 2003PACS: 34.10.+x General theories and models of atomic and molecular collisions and interactions (including statistical theories, transition state, stochastic and trajectory models, etc.) - 34.30.+h Intramolecular energy transfer; intramolecular dynamics; dynamics of van der Waals molecules - 31.70.Hq Time-dependent phenomena: excitation and relaxation processes, and reaction rates     

递变能量成像中最佳X射线管电压预测算法

X射线递变能量成像是依次获取复杂结构件在递变能量下的局部有效信息,并通过多谱融合获取完整结构信息。但是目前的能量选择主要以人工设定管电压步进为主,无法匹配检测对象的有效厚度变化率,成像效率及射线利用率较低。基于递变能量成像规律,提出一种最佳X射线管电压预测算法。该方法通过对检测物体进行变能量预扫描,提取图像序列中有效厚度(高质量区域)和临近厚度(预测区域),建立有效厚度的图像灰度与管电压、X射线光谱之间的物理模型,及临近厚度灰度差与电压的函数模型,进而得到临近厚度最佳成像时的能量预测模型。通过模型求解,实现了能量的自适应预测。以不同厚度钢块为对象,利用该算法逐一预测各个厚度钢块最佳成像时的管电压,并与实际值对比。实验结果显示,在低能时可跨3~4 mm准确预测,高能时可跨7~10 mm预测,精度可以达到95%以上。