Optical orientation effects in the secondary radiation of excitonic molecules

The spectrum of secondary radiation emitted from excitonic molecules under resonant two-photon excitation is investigated theoretically. Taking into account the optical orientation for the final exciton states of the emission process, we derive polarization and angular features of the radiation, reflecting directly the relaxation stage of the molecules.     

Model-based classification of nonstationary vocal fold vibrations

Classification of vocal fold vibrations is an essential task of the objective assessment of voice disorders. For historical reasons, the conventional clinical examination of vocal fold vibrations is done during stationary, sustained phonation. However, the conclusions drawn from a stationary phonation are restricted to the observed steady-state vocal fold vibrations and cannot be generalized to voice mechanisms during running speech. This study addresses the approach of classifying real-time recordings of vocal fold oscillations during a nonstationary phonation paradigm in the form of a pitch raise. The classification is based on asymmetry measures derived from a time-dependent biomechanical two-mass model of the vocal folds which is adapted to observed vocal fold motion curves with an optimization procedure. After verification of the algorithm performance the method was applied to clinical problems. Recordings of ten subjects with normal voice and ten dysphonic subjects have been evaluated during stationary as well as nonstationary phonation. In the case of nonstationary phonation the model-based classification into "normal" and "dysphonic" succeeds in all cases, while it fails in the case of sustained phonation. The nonstationary vocal fold vibrations contain additional information about vocal fold irregularities, which are needed for an objective interpretation and classification of voice disorders.     

The Electron Relaxation to Stationary States in Collision Dominated Plasmas in Molecular Gases

The temporal collision dominated relaxation of electrons to new stationary states, starting from initial stationary states and due to jump-like changes of the electric field, was studied in the plasmas of the molecular gases N₂ and CO. Numerical solving of the time dependent Boltzmann equation for the electrons yields the temporal evolution of their energy distribution function and of resulting macroscopic quantities. The varying relaxation due to different values of the field strength in the final stationary state has been investigated considering the molecules of the plasma only as vibrationally non-excited and, in another case, including the additional impact of collisions with vibrationally excited molecules. The results obtained are discussed and, in particular, the relaxation times found for the transitions to the new stationary states are analysed on the basis of the energy transfer effectiveness by the collision processes. An approximative microphysical basis for the understanding of the main features of the relaxation in such complex molecular gas plasmas could be obtained.     

Inequalities generalizing the second law of thermodynamics for transitions between nonstationary states

We discuss the consequences of a variant of the Hatano-Sasa relation in which a nonstationary distribution is used in place of the usual stationary one. We first show that this nonstationary distribution is related to a difference of traffic between the direct and dual dynamics. With this formalism, we extend the definition of the adiabatic and nonadiabatic entropies introduced by M. Esposito and C. Van den Broeck in Phys. Rev. Lett. 104, 090601 (2010) for the stationary case. We also obtain interesting second-law-like inequalities for transitions between nonstationary states.     

Back focal plane imaging of Tamm plasmons and their coupled emission

The unique optical properties of Tamm plasmons (TPs) – such as flexible wavevector matching conditions including inplane wavevector within the light line, and existing both S‐ and P‐polarized TPs − facilitate them for direct optical excitation. The Tamm plasmon‐coupled emission (TPCE) from a combined photonic–plasmonic structure sustaining both surface plasmons (SPs) and TPs is described in this paper. The sensitivity of TPCE to the emission wavelength and polarization is examined with back focal plane imaging and verified with the numerical calculations. The results reveal that the excited probe can couple with both TPs and SPs, resulting in surface plasmon‐coupled emission (SPCE) and TPCE, respectively. The TPCE angle is strongly dependent on the wavelength allowing for spectral resolution using different observation angles. These Tamm structures provide a new tool to control the optical emission from dye molecules and have many potential applications in fluorescence‐based sensing and imaging.     

The effects of photochemical oxidation and chain conformation on green emission of poly(9,9-dioctylfluorene)

The effects of chain conformation on the photo-oxidation and green emission of poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) has been investigated at both single-molecule and ensemble levels. Single-molecule studies reveal the conformation of PFO chains to be more globular when cast from THF than from toluene solutions. Intensity transients of the single molecules show that the elongated molecules cast from toluene have more fluctuations due to limited energy transfer along the polymer chains. The more globular chains show monotonic decays with isotropic polarization. Emission spectra of the single molecules show that photochemical oxidation leads to a reduction in the emission of the molecule with no change in the emission spectra. No green emission is ever detected for single molecules, indicating that formation of emissive ketone defects is a rare event. Ensemble studies of chains show that molecules cast from THF develop some green emission upon photodegradation, while those cast from toluene do not. The increase in green emission in the globular molecules suggests that interchain contacts improve energy transfer for emissive ketone defects in the PFO cast from THF.     

Phenomenological diffusion laws in solids

A method is considered for study of diffusion in the solid phase, free of the shortcomings of Fick's equations. For the stationary case analytical expressions are obtained for the probability of transmission, reflection, and absorption of diffusing particles by a layer of specified thickness. Principles are formulated for reduction of the nonstationary problem to the stationary case. The results obtained are applied to a study of the kinetics of oxidation processes. A generalization of Fick's first law to the nonstationary case is presented.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 31–36, April, 1979.     

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.     

On the theory of metastable states

It is shown that the stationary states of stochastic systems are stable. Therefore one cannot use the stationary probability distributions for describing the stochastic systems in metastable states. It is shown that the nonstationary stochastic processes can have sample paths with stationary parts. It is proposed to consider these stationary parts as the metastable states.     

单分子尺度的光量子态调控与单分子电致发光研究

分子尺度上的光电相互作用研究可以为发展未来信息和能源技术提供科学基础.扫描隧道显微镜不仅可以用来观察和操纵纳米世界中的原子和分子,而且其高度局域化的隧穿电流还可以被用来激发隧道结中的分子,使之发光,以研究局域场下的分子光电特性.本文综述了中国科学技术大学单分子光电研究组近期在锌酞菁分子电致发光方面取得的科学进展,包括：1）利用有效的电子脱耦合与纳腔等离激元调控技术,实现了隧穿电子激发下的单个锌酞菁分子的电致荧光,并通过发展相关的光子发射统计测量方法,表征了单个分子在隧穿电子激发下的电致荧光具有单光子发射特性;2）发展了具有亚纳米空间分辨的荧光光谱成像技术,实现了对酞菁分子间相干偶极相互作用特征的实空间观察;3）对分子与纳腔等离激元之间的相干耦合作用进行了亚纳米精度的操控,在单分子水平上观察到了法诺共振和兰姆位移效应.这些研究结果不仅为研发基于有机分子的电泵纳米光源与单光子光源等分子光电器件提供了新的思路,而且为在单分子尺度上研究分子光电特性、分子间能量转移以及场与物质之间的相互作用规律等提供了新的表征方法.     

Steady-State and Time-Resolved Fluorescence Polarization Behavior of Acenaphthene

Steady-state and time-resolved fluorescence polarization studies have been carried out on acenaphthene (ACE) in low-temperature glass solutions and at room temperature. In the low-temperature glass the fluorescence polarization values vary considerably with both emission and excitation wavelength. There is a time dependence (on the nanosecond time scale) of the fluorescence anisotropy, r(t), at 77 K, which has a strong dependence upon the excitation and emission wavelengths. Under these conditions, the time-dependent decay of the anisotropy is not attributable to chromophoric motion. The observations are consistent with emission from two closely lying and interconverting excited states. Rate constants for the photophysical processes involved have been determined by fitting the data using a model proposed by Fleming et. al. The results are discussed with particular reference to the care required in using dynamic fluorescence polarization measurements to determine energy transfer rates in systems containing this chromophore.     

EPR of photo-excited triplet states: A personal account

A sketch is presented of the path that has led from Zavoisky’s pioneering experiments to modern investigations by electron paramagnetic resonance (EPR) of the phosphorescent (S = 1) triplet state of polyatomic molecules or ions. The group-theoretical method first introduced by Wigner in his analysis of the multiplets of atomic spectroscopy, likewise provides a key for understanding the zero-field splitting and selection rules for radiative decay of the phosphorescent triplet state. Examples to illustrate the progress made through EPR experiments are selected from three fields. (i) Conformational instability on excitation. Both the zero-field splitting and the electron spin density distribution provide unique fingerprints of a triplet state’s geometry — structural information of a kind that is nonexistent for singlet states! Illustrations are provided by benzene C₆H₆ and fullerene C₆₀. (ii) The optical pumping cycle. The spin selectivity of singlet-to-triplet intersystem crossing and radiative decay of the individual spin components of the triplet state is discussed. In practice this selectivity is put to advantage by performing EPR on triplet states in zero-field by means of optical detection. In turn, such experiments have led to a detailed insight into the spin-orbit coupling mechanisms responsible for the spin selectivity of the above processes. The high sensitivity attainable with optical detection has recently culminated in EPR experiments on single molecules. (iii) Quantum interference. In a triplet state of low symmetry two of the spin sublevels may decay to the ground state by the emission of photons of a common polarization (i.e., out of plane for an aromatic hydrocarbon). In such a situation quantum interference between the two decay channels can be induced by an appropriate preparation of the excited state. An example is shown where flash-excitation in the singlet manifold followed by rapid intersystem crossing causes theS = 1 spin angular momentum to be created in a spin state which is not an eigenstate of the zero-field splitting tensor. This nonstationary character of the initial triplet state, which reflects the spin-orbit coupling pathway, is observed through the detection of a spontaneous microwave signal following the 25 ps laser flash.     

Action of nonstationary linear systems on the time-dependent spectrum of ultrashort light pulses

The spectral and temporal properties of laser light pulses are adequately characterized by the time-dependent spectrum. Response functions are investigated in the frequency as well as in the temporal domain which are suitable for describing the interaction of these pulses with nonstationary (and stationary) systems. The results are applied to physically important systems: the Fabry-Perot étalon, transmission through glass, absorption of molecules, reflection by semiconductors and the optical gate. The conditions are investigated under which the response functions can be measured by applying a square-law detector. An uncertainty relation is formulated for the time-dependent spectrum.     

Attosecond control in photoionization of hydrogen molecules

We report experiments where hydrogen molecules were dissociatively ionized by an attosecond pulse train in the presence of a near-infrared field. Fragment ion yields from distinguishable ionization channels oscillate with a period that is half the optical cycle of the IR field. For molecules aligned parallel to the laser polarization axis, the oscillations are reproduced in two-electron quantum simulations, and can be explained in terms of an interference between ionization pathways that involve different harmonic orders and a laser-induced coupling between the 1sσ(g) and 2pσ(u) states of the molecular ion. This leads to a situation where the ionization probability is sensitive to the instantaneous polarization of the molecule by the IR electric field and demonstrates that we have probed the IR-induced electron dynamics with attosecond pulses.     

Cellular pattern formation in circular domains

An analysis of stationary and nonstationary cellular patterns observed in premixed flames on a circular, porous plug burner is presented. A phenomenological model is introduced, that exhibits patterns similar to the experimental states. The primary modes of the model are combinations of Fourier-Bessel functions, whose radial parts have neighboring zeros. This observation explains several features of patterns, such as the existence of concentric rings of cells and the weak coupling between rings. Properties of rotating rings of cells, including the existence of modulated rotations and heteroclinic cycles can be deduced using mode coupling. For nonstationary patterns, the modal decomposition of experimental data can be carried out using the Karhunen-Loeve (KL) analysis. Experimental states are used to demonstrate the possibility of using KL analysis to differentiate between uniform and nonuniform rotations. The methodology can be extended to study more complicated nonstationary patterns. In particular, it is shown how the complexity of "hopping states" can be unraveled through the analysis. (c) 1997 American Institute of Physics.     

Stationary solutions of the Dirac equation in the gravitational field of a charged black hole

A stationary solution of the Dirac equation in the metric of a Reissner-Nordström black hole has been found. Only one stationary regular state outside the black hole event horizon and only one stationary regular state below the Cauchy horizon are shown to exist. The normalization integral of the wave functions diverges on both horizons if the black hole is non-extremal. This means that the solution found can be only the asymptotic limit of a nonstationary solution. In contrast, in the case of an extremal black hole, the normalization integral is finite and the stationary regular solution is physically self-consistent. The existence of quantum levels below the Cauchy horizon can affect the final stage of Hawking black hole evaporation and opens up the fundamental possibility of investigating the internal structure of black holes using quantum tunneling between external and internal states.     

Optimal trapping wavelengths of Cs2 molecules in an optical lattice

The present paper aims at finding optimal parameters for trapping of Cs₂ molecules in optical lattices, with the perspective of creating a quantum degenerate gas of ground-state molecules. We have calculated dynamic polarizabilities of Cs₂ molecules subject to an oscillating electric field, using accurate potential curves and electronic transition dipole moments. We show that for some particular wavelengths of the optical lattice, called “magic wavelengths”, the polarizability of the ground-state molecules is equal to the one of a Feshbach molecule. As the creation of the sample of ground-state molecules relies on an adiabatic population transfer from weakly-bound molecules created on a Feshbach resonance, such a coincidence ensures that both the initial and final states are favorably trapped by the lattice light, allowing optimized transfer in agreement with the experimental observation.     

Theoretical studies of the atom-dimer polarization transfer

The polarization of alkali atoms in an alkali vapour produced by optical pumping is transferred to the alkali dimers. The effect of this atom-dimer polarization transfer on the internal variables of the atoms and molecules, such as electron spin and nuclear spin, is investigated theoretically in this paper.