Modulational instability of incoherently coupled beams in azobenzene-containing polymer with photoisomerization nonlinearity

The modulational instability of two incoherently coupled beams in azobenzene-containing polymer with photoisomerization nonlinearity is investigated analytically and numerically. Our results show that as a precursor to spatial optical soliton formation, modulational instability can be adjusted and controlled by the wavelength combinations of the signal and background beams. We also discuss the dependences of strength of modulational instability on intensities of two signal beams and background beam. These findings make it possible to predict the formation of incoherently coupled soliton pairs in azobenzene-containing polymer.     

Controllable snail-paced light in biological bacteriorhodopsin thin film

We observe that the group velocity of light is reduced to an extremely low value of 0.091 mm/s in a biological thin film of bacteriorhodopsin at room temperature. By exploiting unique features of a flexible photoisomerization process for coherent population oscillation, the velocity is all-optically controlled over an enormous span, from snail-paced to normal light speed, with no need of modifying the characteristics of the incident pulse. Because of the large quantum yield for the photoreaction in this biochemical system, the ultraslow light is observed even at low light levels of microwatts, indicating high energy efficiency.     

Numerical simulation of the intramolecular dynamics of photoisomerization

The results of mixed quantum-classical and quantum-mechanical numerical calculations of the intramolecular dynamics of photoisomerization under conditions similar to ordinary natural conditions, i.e., for irradiation of the molecule by a light pulse not shorter than the lifetime of the resonant excited electronic state of the molecule and with an intensity comparable to that of solar light at the Earth’s surface, are presented. It was concluded that the dynamics of such photoisomerization should be modeled using quantum-mechanical methods. The simplest approach to modeling the photoisomerization of a molecule with two isomeric forms can be based on the density matrix formalism for describing the interaction of a light pulse with a three-level system of Λ configuration.     

All-optical steering of the interactions between multiple spatial solitons in isotropic polymers

All-optical steering of the nonlinear interactions between multiple spatial solitons can be performed in an isotropic photoisomerization polymer, by propagating an external control beam in perpendicular direction. Fusing, giving birth to another new soliton, and transferring energy can take place in the interactions of signal beams, which can be achieved by changing the incident position of the control beam, the initial relative phase and the power ratio between the signal beams and the control beam. These phenomena are physically explained, and they have significantly potential applications in optical signal readdressing, logic gating, and all-optical switching, etc.     

Optically and thermally induced molecular switching processes at metal surfaces

Using light to control the switching of functional properties of surface-bound species is an attractive strategy for the development of new technologies with possible applications in molecular electronics and functional surfaces and interfaces. Molecular switches are promising systems for such a route, since they possess the ability to undergo reversible changes between different molecular states and accordingly molecular properties by excitation with light or other external stimuli. In this review, recent experiments on photo- and thermally induced molecular switching processes at noble metal surfaces utilizing two-photon photoemission and surface vibrational spectroscopies are reported. The investigated molecular switches can either undergo a trans-cis?isomerization or a ring opening-closure reaction. Two approaches concerning the connection of the switches to the surface are applied: physisorbed switches, i.e.?molecules in direct contact with the substrate, and surface-decoupled switches incorporated in self-assembled monolayers. Elementary processes in molecular switches at surfaces, such as excitation mechanisms in photoisomerization and kinetic parameters for thermally driven reactions, which are essential for a microscopic understanding of molecular switching at surfaces, are presented. This in turn is needed for designing an appropriate adsorbate-substrate system with the desired switchable functionality controlled by external stimuli.     

Photoisomerization processes in the IR-140 laser dye

The photoisomerization processes in the well known IR-140 laser dye and in the closest relevant DTTC model have been investigated by a mode-locked laser spectroscopy in order to observe the influence of a partial rigidization of the polymethine chain. The kinetic, spectral and thermodynamic parameters have been measured; the correlations between the transient quantum yields and the laser efficiency under flash-lamped pumping are discussed. Evidence is given for a surprising solvent effect upon the photoisomerization process.     

Third-order resonant optical nonlinearity from trans–cis photoisomerization of an azo dye in a rigid matrix

 We investigated the trans–cis photoisomerization of an azo dye in a rigid matrix and the resulting third-order resonant optical nonlinearity by means of the simple theoretical prediction of a two-energy-level system, thin-layer chromatography and H-NMR studies. A methylorange (MO), a methylred (MR), congored (CR) or a Disperse Red 1 (DR1) doped polyvinyl alcohol (PVA) or silica film was used as nonlinear optical material. The existence of equi-absorbing points, or isosbestic points in the absorbance spectrum change and the remarkable stationary transmittance to be independent of the action beam intensity enabled us to confirm the photoisomerization even in a rigid matrix. Then, we measured the third-order resonant optical nonlinearity of dichroism through the polarization absorbance spectrum measurement and determined the characteristic optical parameters of the photoisomerization in the film such as the quantum yields φ_T, φ_C, the thermal reaction constant K and the photoisomerization time constant by fitting the theoretical curve of the two-energy-level system to the observed temporal transmittance change after the action beam exposure of the MO/PVA film. The quantum yields were φˉ_T=0.36 and φˉ_C=0.38, respectively. The photoisomerization time constant of MO embedded in the PVA film was a few seconds. The thermal reaction constant K depended on the excitation beam intensity. Received: 20 June 1996/Revised version: 4 October 1996     

光致异构聚合物中相互作用光学空间孤子对的垂直光调控

采用数值法研究了在具有光致异构非线性的聚合物中平行传播的光学空间孤子对(信号光)被另一束垂直入射光调控的情况.调节调控光和信号光的初始相位差、调控光入射位置等可以使信号光孤子产生合成、分开等现象，对此给出了物理解释.这种相互作用的空间光孤子被垂直光调控的现象可望应用于光合成、光互联、光波导等方面. 关键词： 光学空间孤子对 相互作用 垂直光调控 光致异构     

Fluorescence Modulation and Photochromism in Azobismaleimide Derivatives

A fluorophore-photochrome system incorporating an aryleneimine type fluorophore and an azobismaleimide photochrome was developed and the photochemical properties of this system were investigated. The photoisomerization of trans-azoaromatic chromophore leads to the increase of the fluorescence intensity of fluorophore. The cis azobismaleimide isomers revert photochemically to the trans form and the emission intensity decreases. The fluorescence intensity of the imine fluorophore can be modulated under irradiation with UV and visible (436 nm) light due to reversible trans-cis-trans photoisomerization of azobismaleimide partner. The photoisomerization kinetics was obeyed a first-order relationship with a rate constant of 1.95?×?10^?2 s^?1 for azobismaleimide/imine fluorophore system and for polyazothioetherimide/imine derivative the kinetics was described by a biexponential equation.     

Polarization effects in photoisomerization of azo dyes in polymeric films

The reversible cis-trans photoisomerization of disperse red 1 (DR1) in PMMA thin films has been demonstrated previously by using the Attenuated Total Reflection (ATR) method. In this communication photoisomerization of DR1 is shown to be strongly polarization sensitive. This new property of dye doped polymeric films could lead to practical applications in integrated optics. A simple molecular interpretation is given. Illumination of a DR1 sample by polarization fringes produces a grating of molecular orientation able to diffract a probe beam.     

Optical spatial solitons supported by photoisomerization nonlinearity in a polymer

We present a theory for a new type of optical spatial soliton that is based on the angle hole burning mechanism of photoisomerization in some polymers. We predict that the photoisomerization nonlinearity can support steady-state dark and bright spatial solitons in the polymer. We also discuss the dependence of the FWHM of the spatial soliton on wavelengths of the background beams and on the ratio of the intensity of the background beam to that of the signal beam.     

不同基体刚性偶氮化合物光致光学各向异性及其唯象模拟

在不同刚性的聚合物基体聚甲基丙烯酸甲酯（PMMA）、聚乙烯咔唑（PVK）和聚苯乙烯（PS）薄膜基体中掺入相同质量分数（均为0．003）的分散红13（DRl3）偶氮染料。以线偏振连续Ar^＋激光（514nm）作为控制光,连续He-Ne激光（632．8nm）作为信号光考察了具有相同厚度的三种样品在相同控制光功率（15mW）下的光致双折射效应。实验发现刚性较大的聚乙烯咔唑基体样品的双折射效应最小,刚性最小的聚苯乙烯基体样品的双折射效应最大。在偶氮生色团光致异构的四能级模型基础上,建立一新的唯象的模型。在模型中引入描述聚合物基体刚性的参量s,通过数值计算描述了不同基体刚性参量s对偶氮生色团光致异构取向的影响。计算结果表明,基体的刚性越大,样品的光致双折射效应越小,定性地解释了实验现象。     

Isotope separation by selective unimolecular photoisomerization

The selectivity of a photochemical isotope separation process may be preserved in steps subsequent to photoexcitation through the use of unimolecular photoisomerization.     

Mechanisms in adaptive feedback control: photoisomerization in a liquid

The underlying mechanism for Adaptive Feedback Control in the experimental photoisomerization of 3,3'-diethyl-2,2'-thiacyanine iodide (NK88) in methanol is exposed theoretically. With given laboratory limitations on laser output, the complicated electric fields are shown to achieve their targets in qualitatively simple ways. Further, control over the cis population without laser limitations reveals an incoherent pump-dump scenario as the optimal isomerization strategy. In neither case are there substantial contributions from quantum multiple-path interference or from nuclear wave packet coherence. Environmentally induced decoherence is shown to justify the use of a simplified theoretical model.     

Modes selection in polymer mixtures undergoing phase separation by photochemical reactions

Phase separation kinetics and morphology of binary polymer mixtures (A/B) in the presence of photochemical reactions were investigated by using phase-contrast optical microscopy combined with digital image analysis. The polymers were chemically designed in such a way that two types of chemical reactions, intermolecular photodimerization and intramolecular photoisomerization, of polymer segments can be induced and controled by irradiation with ultraviolet light. Unlike the conventional case, the phase separation in the presence of these reactions is spontaneously frozen due to the suppression of the long-wavelength instabilities, resulting in stationary spatial structures with intrinsic periodicities. These characteristic length scales are determined by the competition between the two antagonistic interactions: phase separation as a relatively short-range activation and the photochemical reaction as a long-range inhibition. Furthermore, it was found that the spatial symmetry breaking of concentration fluctuations can emerge from the elastic stress associated with the nonhomogeneous kinetics of the reactions. Experimental data obtained with three types of reactions: A-A only cross-link, A-A and B-B simultaneous cross-links and the reversible A<-->B photoisomerization are described. These results do not only indicate that combination of chemical reactions and phase separation could provide a novel method to control the morphology of multiphase polymer materials, but also suggest that photoreactive polymers can be used as a chemical system to study the mode-selection process in polymers far from thermodynamic equilibrium. (c) 1999 American Institute of Physics.     

Optically switchable all-fiber optic polarization rotator

This study demonstrates an all-fiber optical polarization rotator and switch based on a side-polished fiber (SPF) overlaid with a photoresponsive liquid crystal (LC) containing a nematic LC and a photosensitive azobenzene molecule. The trans-cis photoisomerization of azobenzene modulates the overlaid LC's birefringence, changes the refractive index (RI) of the photoresponsive LC-overlaid SPF, and further controls and switches the phase retardation. This design achieves a 10° phase shift under switching time of less than 1 s. The demonstration has potential for an optically tunable in-line 2 × 2 fiber-optic switch or microstructured fiber-based photonic device controlled by the polarization of light.     

Mathematical modeling of photoisomerization with intramolecular proton transfer

A system of equations describing time changes in the matrix elements of the density operator of a seven-level model of a molecule interacting with a light pulse taking into account spontaneous (including collective) decays of molecule excited states is suggested. Model parameters were selected to allow us to perform modeling of the photoisomerization of a molecule with two isomeric states with different stable proton positions on an intramolecular H-bond by numerically solving the suggested system of equations for density operator matrix elements. An analysis of the characteristic time dependences of the population of states of the model under consideration showed that proton phototransfer in the collective decay of various isomeric states of a molecule in an excited electronic state can be one of effective mechanisms of the photoisomerization of molecules whose structure is described by the model.     

Photochemical behaviour of an acid-terminated azopolymer in solution and in Langmuir–Blodgett films

Trans–cis–trans isomerization processes of an acid-terminated azopolymer have been investigated in mono and multilayered Langmuir–Blodgett (LB) films and the results compared with the behaviour of this azopolymer in solution. UV–vis spectroscopy was used to determine the apparent extent of photoisomerization at the photostationary state, as well as the order and rate constant of the cis → trans thermal isomerization, whilst structural changes of the LB films during photoisomerization have been monitored by AFM microscopy. From these studies it was concluded that the trans → cis photoisomerization extent largely depends on the free volume around the azobenzene chromophores, with the smaller apparent extent of photoisomerization obtained for a well-organized 10-layer LB film. Data also revealed a first-order kinetics for the thermal cis → trans isomerization process of the azopolymer both in solution and in LB films. The cis → trans isomerization process depends on the balance between the stress produced by the larger cross-section of cis-isomers inside the system and the interactions between cis-isomers and neighbouring molecules. The slowest cis → trans isomerization process takes place in a 35-layer LB film, whilst LB films with well-packed azobenzene layers show faster cis → trans isomerization processes.     

Theory of Direct Photoisomerization of Stilbene

A microscopic model for describing the direct trans-cis photoisomerization of stilbene is developed and an interpretation of the experimental results found from time-resolved fluorescence and absorption spectroscopy of stilbene in solution is given. According to this model the photoisomerization of trans-stilbene is proposed to involve the radiationless transition from the trans singlet state S₁(trans), prepared by direct optical excitation, into the perp singlet state S₁ (perp) and the radiationless decay of this state into the quasi-isoenergetic trans triplet state T₄ (trans).     

Site-selective infrared photoisomerizations of 2-fluoroethanol in low-temperature matrices

The Gg′ conformer of 2-fluoroethanol has been isolated in low-temperature noble gas matrices. In high-resolution infrared spectrometry, most vibrational modes exhibit fine structures which are accounted for in terms of multiple trapping sites. The relative intensities of these bands depend on the deposition temperature. Reversible spectral changes with the matrix temperature are observed. Gg′ ? Tt photoisomerizations have been induced from an infrared broad band source irradiation with a rate which depends on the site. The assignments are supported by valence force field calculations on the assumption of a pseudosymmetry for the FCH₂CH₂O fragment. In xenon matrices, the Tt → Gg′ thermal isomerization is observed, for the two main sites, at different temperatures, 25 and 40 K. This result and the difference between the photoisomerization rates suggest that one of the sites is larger than the other. An expected first-order behavior of the photoisomerization process is observed except for a certain site, for which a frequency shift occurs as the photoisomerization proceeds. We propose that very different rate constants govern the molecules embedded in a specific site; reorientations of molecules in their cage may allow the less reactive ones to be photoisomerized, the overall process being limited only by the Tt → Gg′ reverse photoreaction.