Ultrafast Primary Process of Photo-induced N-I Transition and Macroscopic Oscillation of Domain Boundary in TTF-CA

Initial dynamics of photo-induced ionic (I) to neutral (N) phase transition in tetrathiafulvalene- p -chloranil (TTF-CA) was investigated by femtosecond reflection spectroscopy with various excitation intensities. A charge transfer excitation in the I phase produces N donor (D 0 )-acceptor (A 0 ) strings within 2 ps. For a weak excitation intensity, these initial N states decay with a life time of 300 ps at 4 K, but rather multiply leading to macroscopic I-N conversion within 20 ps at 77 K just below the N-I transition temperature T NI . Near T NI , we also found the coherent motion of the macroscopic N-I domain boundary with a period of 85 ps.     

Dynamics of the Photoinduced Ionic-to-Neutral Phase Transition in Tetrathiafulvalene- p -chloranil Studied by Femtosecond Time-resolved Reflection Spectroscopy

Changes in reflection spectra were probed to study the dynamics of photoinduced transformation from ionic to neutral phases in tetrathiafulvalene- p -chloranil crystals. The results have revealed the formation of the precursor of metastable N -phase domains, dynamical lattice relaxation of and proliferation during phase transformation.     

异质二聚体反应中心的电荷转移过程

在低温的状态下,类球红细菌内天然叶绿素的反应中心发生的电荷分离对激发波长有较弱的依赖性,而这种依赖可能来源于分子内电荷转移态。我们采用表现出更多的电荷转移态性质的突变叶绿素为反应中心,对这种电荷分离过程中的激发波长依赖和温度依赖的性质做了进一步的研究。研究发现:突变的异质二聚体存在的两种激发态(定域的激发态与分子内电荷转移态)是相互强耦合的,在突变的分子异质二聚体中形成的电荷转移态并不是电荷分离的有效途径。随着温度的降低,异质二聚体的活性降低,从而电荷分离产率下降。     

香豆素C1F和C2F在醇类溶剂中的激发态溶剂效应

本文在Grabowski模型基础上,提出了一种描述TICT态生成动力学的理论模型,并采用时间相关单光予计数荧光光谱方法,测量了香豆素C1F和C2F在醇类溶剂中的荧光寿命,考察了各种溶剂效应(极性、粘度和温度)对TICT态生成速率的影响,并将结果与DSE关系比较,指出在醇类溶剂中,氢链效应的影响是十分重要的.     

The ionic charge distribution of fission products and the influence of internal conversion on highly preionized heavy ions

At the mass spectrometer LOHENGRIN of the Institut Laue-Langevin the ionic charge state distributions of²³⁵U(n _th,f)-fission products separated according to their mass, nuclear charge and kinetic energy were determined. The mean values and the widths of the ionic charge state distributions are compared with semiempirical predictions. Deviations between the experimental data and the estimation of Nicolaev and Dmitriev are found. Furthermore, the influence of the internal conversion process on the ionic charge state distribution of highly ionized fission products was established. Internal conversion is observed mainly for odd-odd nuclei and nuclei with 59 neutrons. The Auger cascade following the internal conversion process shifts the ionic charge state distribution by about 3 charge units. The yield of conversion electrons per fragment was determined in the mass range 85≦A≦103.     

Ionisation and fragmentation of tetraphenyl iron (III) porphyrin chloride induced by slow multiply charged ion impact

Ionisation and ion-induced fragmentation of tetraphenyl iron (III) porphyrin chloride (FeTPPCl) molecules have been studied after slow collisions (v∼ 0.2 a.u.) with multiply charged ions (O³⁺, Ar⁸⁺). Intact molecules and large fragments are observed in charge states up to q=4. For q=1, the intact molecule is the most abundant species, in particular, when projectiles in higher charge states are used. When the internal energy of the singly charged ion is increased by the energy transfer during the collision, the singly charged system de-excites by the emission of a neutral Cl-atom, a free electron or possibly a negative Cl anion. The processes are observed as direct as well as delayed processes on a μs-time scale. For q=2 to 4 the loss of the Cl-atom and some phenyl groups becomes more likely due to the lower stability and the larger energy transfer. The charge state distribution of atomic fragments is found to be very different, in particular, when C^q+ and Cl^q+ ions are compared. In the first case mainly singly charged ions are detected, whereas in the second case ions in charge states up to q=6 are observed with high intensities. These phenomena are discussed in terms of the intramolecular charge mobility.     

A Comparative Study on the Electronic Structure and Stability of Ti8C12 and V8C12

The electronic structure and stability of dodecahedral Ti₈C₁₂ and V₈C₁₂ clusters are studied and compared with each other by using the discrete-variational local-density functional method. The results show that there exists a nearly-rigid-band-shift rela tion between the electronic structures for the two clusters and that the corresponding bands for them have similar bonding character. Therefore, both clusters can be stable for similar reasons. The results also indicate that there exist two types of charge transfers for both clusters, in which the electrons are found to accumulate to the Ti3d (V3d) and C2p orbitals so that the p-d bonding between the C and Ti (V) atoms is strengthened. Based on the above results, the influence of the charge on the electronic structure and stability of both dusters is examined. FinaUy, the ground-state electronic configurations are obtained for both clusters in the neutral, cationic and anionic charge states. The ground states for the cationic Ti₈C₁₂ and VeCn clusters are found to be nondegenerate. The dodecahedral structures for these two clusters are thus remarkably stable. The rest clusters, i.e., neutral and anionic Ti₈C₁₂ and V₈C₁₂ clusters, have degenerate ground state, and therefore, their structures are expected to undergo Jahn-TeUer distortion further.     

A theoretical study of potential energy curves and spectroscopic constants of VC

Potential energy curves for the various low-lying electronic states of VC have been studied using complete active space multi-configuration self-consistent field (CASMCSCF) followed by first-order and multireference singles and doubles configuration interaction (FOCI, MRSDCI) calculations. The MRSDCI calculations included up to 6 million configurations. Two very low-lying electronic states are found as candidates for the ground state of VC, namely a high spin state ⁴Δ and a low-spin ²Δ state, which is favoured at higher levels. A number of low-lying excited electronic states of VC are predicted, which are yet to be observed. The low-lying electronic states of VC are found to be ionic as inferred from the dipole moments and the charge density calculations. Electron donation and the back-donation process are suggested to be operative in the V-C bond formation.     

Excitation-wavelength Dependent Fluorescence of Ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate

The excitation wavelength dependence of the steady-state and time-resolved emission spectra of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate (EAADCy) in tetrahydrofuran (THF) at room temperature has been examined. It is found that the ratio of the fluorescence intensity of the long-wavelength and short-wavelength fluorescence bands strongly depends on the excitation wavelength, whereas the wavelengths of the fluorescence excitation and fluorescence bands maxima are independent on the observation/excitation wavelengths. The dynamic Stokes shift of fluorophore in locally excited (LE) and intramolecular charge transfer (ICT) states has been studied with a time resolution about 30 ps. The difference between Stokes shift in the LE and ICT states was attributed to the solvent response to the large photoinduced dipole moment of EAADCy in the fluorescent charge transfer state. On this base we can state that, the relaxation of the polar solvent molecules around the fluorophore was observed.     

Theoretical insight into the excited‐state behavior of a novel Compound 1: A TDDFT investigation

In the present work, using density functional theory and time‐dependent density functional theory methods, we investigated and presented the excited‐state intramolecular proton transfer (ESIPT) mechanisms of a novel Compound 1 theoretically. Analyses of electrostatic potential surfaces and reduced density gradient (RDG) versus sign(λ₂)ρ, we confirm the existence of intramolecular hydrogen bond O1‐H2···N3 for Compound 1 in the S₀ state. Comparing the primary structural variations of Compound 1 involved in the intramolecular hydrogen bond, we find that O1‐H2···N3 should be strengthened in the S₁ state, which may facilitate the ESIPT process. Concomitantly, infrared (IR) vibrational spectra analyses further verify the stability of hydrogen bond. In addition, the role of charge transfer interaction has been addressed under the frontier molecular orbitals, which depicts the nature of electronical excited state and supports the ESIPT reaction. The theoretically scanned and optimized potential energy curves according to variational O1‐H2 coordinate demonstrate that the proton transfer process should occur spontaneously in the S₁ state. It further explains why the emission peak of Compound 1‐enol was not reported in previous experiment. This work not only presents the ESIPT mechanism of Compound 1 but also promotes the understanding of this kind of molecules for further applications in future.     

Charge transfer complex formation between TX-100/CCl4 reverse micelle and a series of π-electron acceptors: determination of cmc and aggregation number

Electron donor–acceptor interaction of the reverse micelle (RM) of TX-100 in CCl₄ medium with a number of π-acceptors has been established by analysing the charge transfer (CT) absorption bands in the light of Mulliken's theory. Aggregation number (n) and operational critical micellisation concentration of the RM and formation constants of the RM–p-chloranil and RM-o-chloranil complexes have been determined by UV-visible spectrophotometry. Values of n thus obtained (20–30) are close to that of TX-100/cyclohexane dry reverse micelles determined by other methods and also to a theoretically calculated value of n for AOT/CCl₄ dry RM.     

电子束离子阱对中性气体电荷交换的光谱诊断

在实验室天体物理研究中,电子束离子阱(EBIT)是极端紫外(EUV)和X射线波段能谱分析的重要实验平台,其中EBIT中心残余的中性气体对离子产生存在显著影响。研究了阱区中心残余中性气体对电荷态分布的影响,发现阱区中心残余中性气体和高电荷态离子之间的电荷/能量交换过程不仅影响离子的电荷分布, 而且对激发函数(离子分布比例随电子能量关系曲线)有着极大的影响。利用电离平衡分析方法成功诊断出阱区中心区域残留的中性气体分子数密度,以及内腔室的真空度。     

Effect of iron contamination on grain boundary states at a direct silicon bonded (110)/(100) interface

The effect of iron contamination on the electrical property of a (110)/(100) interfacial grain boundary (GB) in a p‐type direct‐silicon‐bonded wafer has been investigated by current–voltage and capacitance–voltage characteristics. It is found that iron contamination can change the charge property of this “model” GB. Based on proper physical modeling, it is found that compared to a “clean” grain boundary, iron contamination can significantly increase the density of GB states, and the corresponding GB neutral level has also been modified. These results show us a clear physical picture of Fe contamination influencing the GB states. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photo-induced ionic-to-neutral phase transition in tetrathiafulvalen-p-chloranil crystals

Recent experimental results are reviewed of the transformation between ionic and neutral phases in tetrathiafulvalen-p-chloranil crystals, induced by exciting the electronic states of the crystal. Spectroscopic studies have revealed that N phase domains are formed in the ionic-host crystal only above threshold-excitation intensity in the case of charge-transfer excitation; the threshold intensity depends strongly on the wavelength. On the other hand, N-phase domains can be formed without threshold in the excitation intensity in the case of intra-molecular excitation. Also, femtosecond time-resolved study has shown the intensity-dependent dynamics of the N-phase domain formation, and revealed the presence of short-lived intermediate states prior forming the N-phase domain. The mechanism of the photo-induced phase transition in this crystal is discussed based on these results.     

共轭低聚物中光生分子间电荷转移态的第一性原理研究

We perform density functional theory calculations to investigate the polaron pair (charge transfer state) photo-generation in donor-acceptor oligomer methyl-capped (4,7-benzo[2,1,3]thiadiazole-2,6-(4,4-bis (2-ethylhexyl)-4H-cyclopenta[1,2-b;3,4-b'']dithiophene-4,7-benzo[2,1,3]thiadiazole)(CPDTBT).Results show that effective photo-generation of charge transfer state can happen in CPDTBT dimer when the group 4,7-benzo[2,1,3]thiadiazole (BT) in one monomer deviates against the conjugated plane (onset torsion angle is about 20°).The lower excitation energy (530 nm) can only generate the intramolecular excitonic state,while the higher excitation energy (370 nm) can generate the intermolecular charge transfer state,in good agreement with the experiment.Moreover,the mechanism of charge separation in CPDTBT oligomers is discussed.     

Twist Property of Periodic Motion of an Atom Near a Charged Wire

We study the Lyapunov stability of periodic motion of an atom in the vicinity of an infinite straight wire with an oscillating uniform charge, which serves as a mechanism for trapping cold neutral atoms. It is proved by King and Leséniewski that the system has classical periodic motion for a certain range of parameters. In this Letter, we will prove, using the Birkhoff Normal Forms and Morse Twist Theorem, that such a periodic state is of twist type. As a result, besides the stability of the periodic state in the sense of Lyapunov, the system has infinitely many interesting bound states such as subharmonics and quasi-periodic states.     

Initial-Condition Sensitivity and Nonlinear Relaxation in Photo-Induced Ionic-to-Neutral Phase Transition in Tetrathiafulvalen- p -Chloranil Crystals

Recent experimental results of the photoinduced ionic-to-neutral (NI) phase transition in tetrathiafulvalen- p -chloranil (TTF-CA) crystals are reviewed with emphasis on the state-sensitive features and nonlinear properties. Frenkel-type and charge transfer (CT)-type excited states can induce the NI transition but with different characteristics; the transition can be induced only above threshold-excitation intensities in the case of CT excitation, whereas it is induced without any threshold for Frenkel-type excitation. The threshold that implies nonlinear processes of CT excited states is strongly state-dependent and temperature-dependent. Femtosecond time-resolved studies have resolved three distinctive sequential steps in the dynamics; formation of the precursor of N-phase domains, the local proliferation of photoinduced changes, and the process of forming N-phase orders. Origin of the nonlinear processes and the mechanism of the NI transition have been discussed based on these results.     

Observation of atomic spin precessions of isolated fluorine ions on recoil through weak transverse magnetic fields

A new experimental method for studying the hyperfine interactions of multi-electron configurations in isolated ions is illustrated for fluorine using the long-lived 197 keV¹⁹F(5/2⁺) state as probe. The observed atomic precessions were found to vary linearly with the applied weak magnetic field integrated over the flight path of the recoiling ions. The data are well accounted for, assuming configurations from the coupling of 2s and 2p electrons in the relevant ionic charge states.     

Characterizing neutral modes of fractional states in the second Landau level

Fractionally charged quasiparticles, which obey non-abelian statistics, were predicted to exist in the ν=8/3, ν=5/2, and ν=7/3 fractional quantum Hall states (in the second Landau level). Here we present measurements of charge and neutral modes in these states. For both ν=7/3 and ν=8/3 states, we found a quasiparticle charge e=1/3 and an upstream neutral mode only in ν=8/3-excluding the possibility of non-abelian Read-Rezayi states and supporting Laughlin-like states. The absence of an upstream neutral mode in the ν=7/3 state also proves that edge reconstruction was not present in the ν=7/3 state, suggesting its absence also in ν=5/2 state, and thus may provide further support for the non-abelian anti-pfaffian nature of the ν=5/2 state.     

Laser illumination for manipulation of hydrogen charge states in silicon solar cells

This Letter investigates the important parameters of illumination for control of hydrogen charge states in p‐type silicon solar cells. Through variations in the wavelength and intensity of illumination, evidence is provided for the importance of the neutral charge state of interstitial hydrogen, H⁰, for the passivation of defects in upgraded metallurgical grade (UMG) silicon. It is shown that through this approach minority carrier lifetimes may be achieved in excess of those realised through previous techniques, resulting in open‐circuit voltages (iV_OC) over 710 mV. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)