Semiphenomenological analysis of cis-to-trans isomerization of polyacetylene

Semiphenomenological analysis of cis-to-trans isomerization process of polyacetylene is presented. It is shown that excitation of cis-transoid form to trans-cisoid form is necessary in the course of the isomerization. The probability of tunneling of a π electron from trans-cisoid to cis-transoid state is estimated to be about 0.7 per second. The life time of trans-cisoid form can be inferred to be several hours.     

Isomerization and fluorescence characteristics of sterically hindered azobenzene derivatives

We report synthesis and isomerization behaviors of sterically hindered azobenzene derivatives (1 and 2) with decyloxy and hydroxy groups, respectively, and their fluorescence enhancement under UV light irradiation characterized by means of absorption and fluorescence spectroscopy measurements. Upon irradiation of as-prepared solution (1) with UV light (∼200 mJ/cm²) a cis-rich photostationary state was reached. Obviously different from 2 showing very fast thermal cis-to-trans isomerization within 2 min, slow cis-to-trans thermal back isomerization of 1 with a long alkyl chain at ambient temperature was observed on the time scale of weeks. In contrast to no striking changes in absorption and fluorescence spectra of compound 2, the azobenzene 1 showed green fluorescence upon prolonged irradiation with UV light (about 3-8 J/cm² exposure doses), although both the initial trans-rich and cis-rich states of azobenzene molecules were not fluorescent in solution. The stability of fluorescence efficiency caused by drying and redissolving processes was examined.     

A semiclassical dynamics study of the photoisomerization of methyl-substituted azobenzene

A semiclassical dynamics simulation study is reported for a trans–cis photoisomerization cycle of four azo compounds, including azobenzene, 2-methylazobenzene, 2,6-dimethylazobenzene, and 2,2′-dimethylazobenzene. For both trans?→?cis and cis?→?trans isomerization processes, each compound is excited by a 50?fs (fwhm) laser pulse with a photon energy leading to a ππ* excitation. It is found that the compound in both cases follows a rotational path from reactant to product and that the isomerization dynamics is significantly affected by substitution. The relative times for completing a trans–cis isomerization cycle for four compounds, 2,6-dimethylazobenzene?>?2,2-dimethylazobenzene and 2,6-dimethylazobenzene?>?2-methylazobenzene>?azobenzene, follow the same order as for the photoinduced formation of the surface relief grating of polymers based on these four compounds. The simulation results provide a basis for understanding the surface relief grating formation of azobenzene-based materials upon irradiation with laser beams.     

Photoelectrochemical switch based on cis-Azobenzene chromophore modified TiO2 nanowires

Carboxylated-azobenzene chromophore modified TiO₂ nanowire composites were prepared and characterized. Photocurrent measured with monochromatic incident light irradiation results showed that azobenzene modified TiO₂ nanowire electrode had obviously higher photocurrent and broader visible light response covering range of 350-650 nm, and the wavelength position corresponding to the maximum photocurrent was red shift to about 470 nm. After alternate irradiation with UV and visible light, the azobenzene modified TiO₂ nanowire electrode exhibited obvious photoelectrochemical switching properties. Furthermore, the photocurrent under visible light irradiation was much higher than that under UV irradiation due to the cis-to-trans isomerization transformation of azobenzene chromophore.     

Pyrolysis of amines: Infrared spectrum of allylimine

Infrared absorption spectrum of allylimine in the gas phase was measured for the first time. The spectrum consisted of two rotational isomers, cis and trans, around the CC bond. The relative population of the trans form was 70–80%, and the rest was for the cis form at room temperature. This intermediate molecule was produced by the thermal decomposition of diallylamine and by the isomerization of propargylamine. The vibrational assignments were made with the help of an ab initio MO calculation. The half-life in the absorption cell was about 20 min.     

Kinetic analysis of the photochemically and thermally induced isomerization of an azobenzene derivative on Au(111) probed by two-photon photoemission

Two-photon photoemission (2PPE) spectroscopy is employed to quantify the photochemically and thermally induced trans ⇌ cis isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on an Au(111) surface. The isomerization of TBA is accompanied by significant changes in the electronic structure, namely different energetic positions of the lowest unoccupied molecular orbital of both isomers and the appearance of an unoccupied final state for cis-TBA. A quantitative analysis of these effects allows the calculation of cross sections for the reversible isomerization and determination of the ratio between both isomers in the photostationary state, where 55±5% of the molecules are switched to cis-TBA. The cross section for the photoinduced trans → cis isomerization is 3.3±0.5×10⁻²² cm², while for the back reaction, a value of 2.7±0.5×10⁻²² cm² is obtained. Furthermore a pronounced reduction of the activation energy by a factor of four compared to the free molecule is found for the thermally activated cis → trans isomerization of the surface-adsorbed TBA. This demonstrates that the potential energy landscape of the adsorbed TBA is remarkably different from the liquid phase.     

An ab initio study of the geometries,anharmonic force fields and fundamental vibration frequencies of cis- and trans-formic acid

The geometry, harmonic and anharmonic force fields, and fundamental vibration frequencies of cis- and trans-formic acid are studied ab initio in the 4–31G and (9,5) basis sets. For the more stable trans-conformer (i.e., trans with respect to CH and OH) comparisons are made between the predicted and observed anharmonic frequencies, and between the calculated harmonic force constants and those Redington derived from an analysis of experimental data. In the case of the less stable cis-conformer, for which there is as yet little experimental data, the calculations serve to predict values for the fundamental vibrational frequencies.     

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.     

A multichannel Raman spectrometry study of polyacetylene isomerization induced by laser irradiation

The multichannel Raman spectrometry has been used in the study of the isomerization reaction of an 80% cis PA film into a trans PA, using a laser beam for a double purpose. It is employed simultaneously as an activation agent inducing the isomerization reaction and the Raman diffusion. In each experience, the power of the laser beam Pⁱ(λ) was equivalent to the temperature. Twelve spectra have been recorded at different time periods tj = j·dt. The integrations of the Raman intensities related to two selected bands were numerically calculated.We also proposed an original method for the determination of the isomeric composition. A quantitative relationship between the equilibrium temperature and the laser beam power (in the range of laser power: 30 < Pⁱ(λ) < 300 mW) has been found. An estimate number of isomerized molecules N₀ and then a correction factors f_cis and f_trans were also obtained.     

Rotational Spectra of cis-HCOOH, trans-HCOOH, and trans-HCOOH

While the rotational spectrum of trans-HCOOH is well known, the cis-rotamer was known previously only from a few microwave transitions. The spectra of cis- and trans-HCOOH and of trans-H¹³COOH have been identified in the far infrared Fourier transform spectrum recorded in the range 20-100 cm⁻¹. The measurements were performed using an 80-cm base length White-type multipass absorption cell in combination with a Bruker IFS 120 HR spectrometer. The White cell was set up for 90 passes (total path length=72 m) and the spectrum was measured with a resolution (FWHM) of 0.0012 cm⁻¹. Submillimeter-wave transitions, just under 1 terahertz, of the same three species of formic acid were measured in the range from 835 to 993 GHz (27.8-33.1 cm⁻¹) and it was possible to assign b-type Q-branch transitions of both cis- and trans-HCOOH in this region, and also transitions of trans-H¹³COOH. These measurements served furthermore as a check on the calibration of the FTIR measurement. Furthermore, new millimeter-wave measurements in the range 172-366 GHz were made, bridging the gap between the MW and FIR lines for cis-HCOOH and providing important data for trans-H¹³COOH. The assigned FTIR, submillimeter- and millimeter-wave data reported in this work were fitted together with previously published rotational transitions to obtain rotational constants, using Watson's A-reduced Hamiltonian, for cis-HCOOH, trans-HCOOH, and trans-H¹³COOH.     

Behavior of Sodium Lauroyl Sarcosinate in Solution and Binary Mixtures by Means NMR

Measurements of the ¹H and ¹³C chemical shifts as well as ¹H spin–lattice relaxation times of sodium lauroyl sarcosinate (SLAS) in aqueous solutions and mixed binary systems with co-surfactants were carried out at various concentrations. It will be shown that changes in the chemical shifts for the N–CH₂ groups in SLAS with increasing surfactant concentration can be used to estimate the ratio p _cis /p _trans of cis- and trans-isomers. The relative fraction p _trans of molecules in trans-configurations increases the most in a narrow concentration range 0.007–0.034 mol/l, i.e., at the transition from the monomeric state to the micelle. The ratio p _cis /p _trans asymptotically decreases with increasing concentration, reaching a constant value at concentrations significantly above the critical micelle concentration. Thus, the ratio can be related to the process of micellization. If micellization takes place, the cis-isomer starts to transform into trans-isomer because the trans-isomer is more favorable in micelles. Because of the smaller cross section of the polar group region, the trans-conformation can be more easily incorporated into the micelle. In summary, the occurrence of micellar aggregates at low SLAS concentration in mixed systems can be clearly inferred from the nuclear magnetic resonance spectra.     

Enthalpies of formation and isomerization of cis‐ and trans‐decalin,and their oxa‐analogs by G3(MP2)//B3LYP calculations

G3(MP2)//B3LYP calculations have been carried out on trans‐ and cis‐decalin, and their mono‐, di‐, tri‐, and tetraoxa‐analogs. The main purpose of the work was to obtain enthalpies of formation for these compounds, and to study the relative stabilities of the cis–trans and positional isomers of the various (poly)oxadecalins. Comparison of the computational enthalpies of formation with the respective experimental ones, known only for the decalins and 1,3,5,7‐tetraoxadecalins, shows that in both cases the computational values are more negative than the experimental ones, the deviations being ?5 to ?7 kJ mol^?1 for the decalins and ?12 to ?17 kJ mol^?1 for the 1,3,5,7‐tetraoxadecalins. The respective computational enthalpies of cis–trans isomerization, however, are in excellent to satisfactory agreement with the experimental data. The cis–trans enthalpy differences vary from +11.0 kJ mol^?1 for decalin to ?15.4 kJ mol^?1 for 1,4,5,8‐tetraoxadecalin. Low relative enthalpy values were also calculated for the cis isomers of 1,8‐dioxadecalin (?3.7 kJ mol^?1), 1,3,6‐trioxadecalin (?4.6 kJ mol^?1), 1,3,8‐trioxadecalin (?9.7 kJ mol^?1), 1,4,5‐ trioxadecalin (?5.6 kJ mol^?1), 1,3,5,8‐tetraoxadecalin (?7.3 kJ mol^?1), and 1,3,6,8‐tetraoxadecalin (?14.5 kJ mol^?1). Copyright © 2009 John Wiley & Sons, Ltd.     

Stability of all-trans-β-carotene under ultrasound treatment in a model system: Effects of different factors,kinetics and newly formed compounds

The effects of factors and kinetics of all-trans-β-carotene degradation under ultrasound treatment in a model system were investigated. The compounds of degradation were also tentatively identified by HPLC-DAD, Raman and FT-IR spectroscopy. The type of solvents and temperature were important factors in determining the degradation reaction. Liquid height, ultrasonic intensity and duty cycle of ultrasound exposure only affected the rate of degradation but did not change the nature of degradation. Degradation rate of β-carotene in dichloromethane was the highest. Degradation rate of β-carotene decreased with increasing of temperature. Degradation kinetics of all-trans-β-carotene under ultrasound fitted first-order reaction at ?5 to 15 °C, and fitted second-order reaction at 25 °C. Degradation products included isomers: 15-cis-β-carotene, di-cis-β-carotene and other compounds with function group of C–O.     

Thermally induced variations in the conformational composition and spatial orientation of molecular components of a dicarbocyanine dye layer

The effect of heating on the spatial orientation and concentration of the components of dicarbocyanine dye layers on a glass substrate is studied experimentally. Layers of two types differing in the spatial orientation angles of all their components (monomeric all-trans and β-mono-cis isomers, dimers, and J aggregates) are considered. It is shown that storing of samples at temperatures of 150–200°C causes partial thermal destruction but does not change the absorption spectra of the molecular components. Heating of the layer of the first type changes neither the orientation nor the relative concentration of the components. Heating of the layer of the second type leads to irreversible changes in the orientation angles of all the molecular components and causes the β-mono-cis isomer and the dimer to transform into the all-trans isomer and the J aggregate. The dependences of the orientation angle on the heating time have the form of saturating functions. The rate of variation of the orientation angle and its limiting value in the saturation region increase with increasing temperature of heating. At high temperatures, the layer of the second type transforms completely into the layer with the first type of spatial orientation. A mechanism of the changes in the angles of the spatial orientation of the layer components, which includes the stages of thermal isomerization and reorientation of each molecular component, as well as rearrangement of its environment, is proposed. Energetic and kinetic parameters of all the stages of layer reconstruction satisfying the experimental results obtained in the region from 150 to 230°C are determined.     

Vibrational analysis of the Raman spectra of polycrystalline cis-2-butene

The vibrational assignments and potential energy distributions for cis-2-butene were examined by transferring appropriate force constants from trans-2-butene and the model systems, cis-1,2- and trans-1,2-difluoroethylene. The model fluoroethylene systems provided both the crucial interaction force constants, which account for effects across the double bond in cis-2-butene, and the skeletal out-of-plane force constants. The zero-order frequencies calculated for cis-2-butene from the transferred potential function agreed quite well with the low temperature Raman spectra of the polycrystalline material.     

Production and microwave spectra of dithioformic acid,HCSSH

Hitherto unknown dithioformic acid, HCSSH, has been produced by pyrolysis (300°C) of methanetrithiol, HC(SH)₃, and identified by the microwave spectrum (18–40 GHz) of its most abundant species H¹²C³²S³²SH. Rotational transitions of this species in its ground state have been assigned to a trans and a cis rotamer. Both rotamers are planar, the trans conformer being the more stable by ca. 350 cm^?1 mole^?1. For each rotamer spectra of molecules in two vibrationally excited states have been assigned. Frequencies of transitions of importance for search for HCSSH in interstellar space are reported.     

Quantitative time-resolved EPR CIDEP study of the photodecomposition oftrans-azocumene in solution

The cumyl radical system, which is created after laser flash irradiation oftrans-azocumene in benzene solution at room temperature, is investigated using time-resolved EPR spectroscopy. From the quantitative analysis of EPR time-profiles at different microwave powers the spin relaxation timesT ₁=3.5±0.3 μs andT ₂=2.5±0.1 μs are evaluated as well as the magnitude of the chemically induced electron polarization (CIDEP), which is generated by the radical pair mechanism (RPM). The geminate RPM polarization is found to be considerably smaller than the F-pair one, 32±2 and 48±5 in units of the Boltzmann polarization, respectively. This is attributed to an initial radical separation in the geminate pair, caused by the cleavage reaction. Besides cleavage, the photoexcitedtrans-azocumene also decays via isomerization to the thermally unstablecis-isomer, the lifetime of which is found to be 14±3 μs at 293 K in benzene, three times longer than in cyclohexane. The quantum yield of free radicals, escaping from the primary cage, is determined as 0.28±0.06 for the decay of the excitedtrans-azocumene and 0.18±0.04 for the thermal cleavage of thecis-isomer. The self-termination of cumyl radicals proceeds with a rate constant 2k _t=7±1)·10⁸ M^?1s^?1 in benzene at RT.     

Time-resolved studies on the photoisomerization of a phenylene-silylene-vinylene type compound in its first singlet excited state

In femtosecond laser-flash photolysis experiments, the first singlet excited state of trans-ST, ((E,E)-{1,4-bis(2-dimethylphenylsilyl)ethenyl}benzene) showed a strong S1(π,π^?)-Sn absorption band at 540 nm in acetonitrile and at 550 nm in hexane. The lifetime of this state was determined to be 13.2±2.0 and 11.1±1.5 ps, respectively. Intersystem crossing was shown not to be a principal route for the deactivation of this S1 state of trans-ST. Evidence for this conclusion involved two complementary nanosecond laser-flash photolysis experiments. In one experiment involving direct excitation, no transient absorption spectrum was detected in the 350-650 nm spectral range. Yet, in the second experiment, on triplet sensitization, using xanthone, a transient absorption at 400 nm was tentatively assigned to the triplet state absorption of trans-ST. Photoisomerization was monitored in nanosecond time-resolved bleaching experiments. From these experiments the trans-cis photoisomerization quantum yield was determined to be 0.23 on direct trans-ST excitation. In a xanthone-sensitized stationary-state excitation experiment, the trans-cis isomerization quantum yield was determined to be 0.32. The main deactivation route of trans-ST in its S1 state is repopulation of the ground state directly through internal conversion or with the intermediacy of conformers with twisted geometry.     

Specific heats of pure and doped polyacetylene

The temperature dependences (0.8 K ? T < 7 K) of the specific heats of pure polyacetylene (both $\text{cis}$ and $\text{trans}$ isomers) and heavily doped metallic [CH(AsF₅)_0.12]_X are reported. Results for undoped $\text{cis}$-(CH)_X indicate behavior typical of crystalline polymers, whereas isomerization to the $\text{trans}$-form leads to a small term linear in temperature signifying increased disorder. Comparison of the data from $\text{cis}$ and $\text{trans}$ starting material indicates that isomerization is induced during doping. The increased coefficient of the linear term in the metallic polymer is discussed in terms of two contributions; an electronic term expected for a metal, and the increased effect of disorder in the doped polymer.     

Photo-induced isomerization of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene ultra-thin solid film prepared by Langmuir–Blodgett technique

The photo-induced response of an ultra thin polymeric film of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene (P5) is investigated. A monolayer of P5 at a gas–water interface possesses a mean molecular area of 28.0 Å²/monomer-repeat. Multilayer films of P5 were prepared by horizontal deposition at a surface pressure of 25 mN/m². The uniformity of the transfer process is shown by UV–vis absorption spectra where a linear relationship between the absorption maxima and the number of transferred layer was observed. The average layer thickness of the transferred film determined by XRD measurements is 34.0 Å. This is longer than the length of the azobenzene side group. The transferred film shows a blue shift of the π–π¹ transition from 357 nm for the P5 in solution to 340 nm for the P5 in the film. This suggests the formation of H-aggregate with a head-to-head arrangement of the dipole within the film. The optical property of the transferred film is changed by the irradiation of the film with the UV light at 385 nm. An irreversible change in its molecular packing in the film is seen in the shift of the UV–vis absorption maxima and the change in morphology as observed by AFM. The film morphology changes from being a smooth film into an island-like surface when exposed to the UV irradiation. The layer structure in the film is destroyed. A mass transport is observed during the cis–trans thermal back isomerization process. This suggests that movement of the P5 took place in both the trans–cis isomerization process and the cis–trans back isomerization process. The first movement leads to a molecular expansion while the second, to a molecular contraction.