Structural change in the photoexcited cis-polyacetylene

The structural change in the cis-polyacetylene photoexcited with the energy corresponding to its band gap was examined. The growth of four new infrared absorption peaks at 802, 1062, 1112 and 1259 cm^?1 were found after the irradiation. The appearance of these peaks strongly suggests the formation of the trans-cisoid segment in the cis-transoid chain of polyacetylene.     

PMR investigation of the structure of native and iodine doped polyacetylene films

The second moment of the proton magnetic resonance line of native cis- polyacetylene, thermally isomerized trans-polyacetylene, and iodine doped initially cis-polyacetylene has been measured by a pulse technique. The results differ qualitatively and quantitatively from previous reports. They are discussed in terms of the proposed crystalline structures of (CH)_x.     

First principles study of the electron transport through cis-polyacetylene based molecular wires

The electron transport properties of cis-polyacetylene and cis-polyacetylene based molecular wires (oligo(cyclopentadiene), oligo(pyrrole), and oligo(furan)) have been studied theoretically using a combination of density-functional theory and non-equilibrium Green′s functions method. The results demonstrate that the introduction of bridging group X (X=CH₂, NH, and O) in cis-polyacetylene has a profound effect on the electron transport behavior of the molecules. The conductance of the four molecular wires decreases in the order of polyacetylene>oligo(cyclopentadiene)>oligo(furan)>oligo(pyrrole). In particular, the conductances of oligo(furan) and oligo(pyrrole) are much lower than those of polyacetylene and oligo(cyclopentadiene). The mechanism of this difference of electron transport properties of these four molecular systems is analyzed in terms of their geometric structures, electronic structures, transmission spectra, and spatial distribution of frontier orbitals. It is found that the energy levels of frontier molecular orbitals and the evolution of spatial distribution of frontier molecular orbitals with the applied bias are the essential reason for generating this difference of electron transport behaviors of the four molecular systems.     

The electronic structures of cis-polyacetylene

The electronic structures of two possible forms of the so-called $\text{cis}$-skeletal polyacetylene ($\text{cis}$-polyacetylene) are investigated on the basis of the tight-binding LCAO-SCF-MO method under the CNDO/2 version. The analyses of the total energies per unit cell, the π bond orders and the interatomic interaction energies as to the both forms predict the $\text{cis}$-transoid backbone for the $\text{cis}$-polyacetylene. The examination of the patterns of particular molecular orbitals of the hypothetical $\text{cis}$-polymer with equal C-C bond lengths also supports the $\text{cis}$-transoid form.     

The infrared and Raman spectrum of trans-polyacetylene: A self-consistent-field study

Using force constants which have been obtained for the first time from semi-empirical self-consistent-field calculations on various cluster models of periodic trans-polyacetylene and of neutral and charged soliton and polaron defects the infrared and Raman spectrum of undoped and doped trans-polyacetylene is analyzed and interpreted.     

Microwave emulations and tight-binding calculations of transport in polyacetylene

A novel approach to investigate the electron transport of cis- and trans-polyacetylene chains in the single-electron approximation is presented by using microwave emulation measurements and tight-binding calculations. In the emulation we take into account the different electronic couplings due to the double bonds leading to coupled dimer chains. The relative coupling constants are adjusted by DFT calculations. For sufficiently long chains a transport band gap is observed if the double bonds are present, whereas for identical couplings no band gap opens. The band gap can be observed also in relatively short chains, if additional edge atoms are absent, which cause strong resonance peaks within the band gap. The experimental results are in agreement with our tight-binding calculations using the nonequilibrium Green's function method. The tight-binding calculations show that it is crucial to include third nearest neighbor couplings to obtain the gap in the cis-polyacetylene.     

ac Conductivity of semiconducting trans-polyacetylene

The ac conductivity of semiconducting trans-polyacetylene has been measured over the frequency range 10 Hz to 10 MHz at room temperature. Both ohmic and blocking contacts were used on samples prepared at several doping levels below the metallic limit. The complex conductivity was found to be frequency independent for all levels of doping and for both types of contacts. A discussion is given regarding soliton motion and inhomogeneous doping and their possible effects on ac conductivity in trans-polyacetylene.     

High resolution 13C NMR in undoped cis- and trans-polyacetylene

We have applied ¹³C cross-polarization (CP) powder- and MAS-NMR to cis- and trans-polyacetylene. All three elements of the chemical shift tensor (σ₁₁, σ₂₂, σ₃₃) were determined in p.p.m. with respect to TMS as: (a) Cis; σ₁₁ = ?228, σ₂₂ = ?139, σ₃₃ = ?17; (b) Trans; σ₁₁ = ?234, σ₂₂ = ?146, σ₃₃ = ?34.     

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.     

Electronic spectra of carotenoids. β-Carotene

Linear dichroic spectra of rans- and cis-β-carotenes in stretched polyethylene films have been reexamined. Self-consistent assignments of the major absorption bands have been made on the basis of polarization directions and molecular orbital predictions. The angle between the ¹B ← A and ¹C ← A transition moments in cis-β-carotene is very near 90δ.     

Pyrolysis of amines: Infrared spectrum of ethylideneimine

The gas-phase infrared absorption bands of ethylideneimine were detected in the pyrolysis products of ethylamine, isopropylamine, diethylamine, diisopropylamine, and five other amines. The spectrum is characterized by doublets, reflecting the existence of cis and trans rotational isomers. The half-life in the absorption cell at room temperature was about 18 min. The force constants of both isomers are calculated by an ab initio MO method.     

Free carrier absorption in quantizing magnetic fields: Nonpolar optical phonon scattering

A quantum theory of free carrier absorption in nondegenerate semiconductors and in strong magnetic fields which was previously developed to treat the case when acoustic phonon scattering dominates the free carrier absorption process [1] is extended to treat the case when nonpolar optical scattering is important. When the electromagnetic radiation field is polarized parallel to the direction of the applied magnetic field, results are obtained which are similar to those when acoustic phonon scattering is dominant. The free carrier absorption is an oscillatory function of the magnetic field which on the average increases in magnitude with the magnetic field. However, more structure in the free carrier absorption occurs when nonpolar optical phonon scattering dominates. This is due to the fact that there are two periods in the oscillatory magnetic field dependence associated with the emission or the absorption of optical phonons during the intraband transitions. When the cyclotron frequency exceeds the sum of the photon and optical phonon frequencies, i.e. ω_c > θ + ω_o, the free carrier absorption is predicted to increase linearly with magnetic field when ?ω_c? k_BT. The magnetic field dependence of the free carrier absorption can be explained in terms of phonon-assisted transitions between the various Landau levels in a band involving the emission and absorption of optical phonons.     

Modeling of CN-functionalized silica as vehicle for delivery of the chemotherapeutic agent: cisplatin

The adsorption of cisplatin and its complexes, cis-[PtCl(NH₃)₂]⁺ and cis-[Pt(NH₃)₂]²⁺, on a CN-functionalized SiO₂(111) surface has been studied by the atom superposition and electron delocalization method. The adiabatic energy curves for the adsorption of the drug and its complexes on the delivery system were considered. Electronic structure and bonding analyses were also performed. The molecules are adsorbed on the functionalized surface resulting in a major absorption of the cis-[Pt(NH₃)₂]²⁺ complex. The molecule?Csurface interactions are strengthened due to the incorporation of the CN silane group. The most important bonds occur through Pt?CC, Pt?CN and Pt?CSi interactions. Despite the new interactions, the functionalized carrier maintains its matrix properties after adsorption. The remarkable properties may be attributed to the small electronic structure changes in the Si?CCN groups caused by the interaction with neighboring cisplatin molecules and the enhancement in Pt-bonding interactions due to the surface incorporation of the CN silane groups.     

Peierls distortion and vibrational spectra in undoped and doped trans-polyacetylene

We analyze the conditions under which the vibrational spectrum can provide information on the existence of the Peierls distortion in undoped trans-polyacetylene. If in the doped material sections of undimerized chains are generated, calculations predict a Raman active A_g band approximately between 1300-1250 cm^?1.     

Probe into the reflection from GaP nanoparticles via different solutions of radiative transfer equation

The reflection and absorption spectra of gallium phosphide (GaP) nanoparticles were measured. The radiative transfer equation (RTE) for the medium with scattering and absorption is solved by three different solutions. The ratio of the absorption and scattering coefficients (E _a/E _s) of the GaP nanoparticles layer is calculated from the reflection spectrum via the three solutions, respectively, and the result derived with the three-flux model is closest to the exact solution given by Giovanelli. The E _a/E _s curves all exhibit the energy band gaps of GaP nanoparticles, which are consistent with the absorption spectrum measurement. The shape of the reflection spectrum is mainly determined by the absorption, and the scattering only influences its intensity. The energy band structure of the powder sample plays an important role in the reflection phenomenon, and the reflectance data can be used for quantitative analyses.     

Vibrational spectroscopy of trans and cis deuterated formic acid (HCOOD): Anharmonic calculations and experiments in argon and neon matrices

The absorption spectra of trans and cis conformers of deuterated formic acid (HCOOD) isolated in argon and neon matrices are analyzed in the mid-infrared and near-infrared spectral regions (7900-450 cm⁻¹). Vibrational excitation by narrow-band IR radiation is used to convert the lower-energy trans conformer to the higher-energy cis form. A large number of overtone and combination bands are identified. The results of anharmonic vibrational calculations (CC-VSCF) for both conformers are reported and compared to the experimental spectra.     

Quantum-chemical study of the spectral properties of stilbene isomers

Calculations of absorption spectra of cis-and trans-forms of stilbene by the quantum-chemical method of intermediate neglect of differential overlap with spectroscopy parametrization were carried out. The electron structure of a stilbene molecule was studied and energy-level diagrams were drawn and analyzed. Rate constants of different photophysical processes occurring in a stilbene molecule after absorption of a photon were calculated in relation to the molecule conformation. On the basis of the obtained results, possible configurations of photoisomer molecules were considered and the most probable configurations of excited stilbene molecules were determined. It was shown how the change in the configurations of cis-and trans-forms of stilbene affects its spectral properties.     

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.     

Exciton-phonon interaction in mixed silver halides: Resonant Raman scattering vs photoluminescence

An investigation of resonant Raman scattering in mixed crystals of AgBr:Cl at 1.8 K shows that the zero-phonon and LO phonon-assisted exciton luminescence excited in the free indirect exciton absorption, exhibits an anomalous dependence on the exciton photon energy E_L. Close to the exciton gap, the bands show a Raman-like behaviour with their peaks at constant energetic distance from E_L. As E_L is tuned further into the absorption, the bands gradually develop into normal photoluminescence. The effect is explained by taking into account exciton relaxation via scattering by long-wavelength acoustic phonons, a process which is strongly energy dependent. In addition, resonant Raman scattering observed for excitation in the zero-phonon absorption suggests study for the first time of the mode behaviour of certain off-zone center phonons in this system.     

Effects of strong electric fields in a polyacetylene chain

In this work, we study the effects related to the creation of electron/hole pairs via application of an external electric field that acts on a pristine trans-polyacetylene molecular chain at zero-temperature. This phenomenon is termed Schwinger–Landau–Zener (SLZ) effect and arises when a physical system, which can even be the vacuum, is under the action of a strong, static and spatially homogeneous electric field. Initially, we investigate how the electrical conductivity of the polyacetylene changes with the applied field, by considering the carriers production as well as the variation of the interband gap according to certain ab initio models. Next, we analyse the competition between the SLZ effect and another one associated with the incidence of an uniform electric field on one-dimensional crystals – the Bloch oscillations. We evaluate the conditions in which these latter can be destroyed by the particles created through the same field that induces them, and verify the possibility of occurrence of the Bloch oscillations inside the trans-polyacetylene with frequencies equal to or higher than the terahertz scale.