The photoisomerization mechanism of azobenzene: a semiclassical simulation of nonadiabatic dynamics

We have simulated the photoisomerization dynamics of azobenzene, taking into account internal conversion and geometrical relaxation processes, by means of a semiclassical surface hopping approach. Both n-->pi* and pi-->pi* excitations and both cis-->trans and trans-->cis conversions have been considered. We show that in all cases the torsion around the N==N double bond is the preferred mechanism. The quantum yields measured are correctly reproduced and the observed differences are explained as a result of the competition between the inertia of the torsional motion and the premature deactivation of the excited state. Recent time-resolved spectroscopic experiments are interpreted in the light of the simulated dynamics.     

QM/MM connection atoms for the multistate treatment of organic and biological molecules

We present an extension of our semiempirical floating occupation MO-CI approach for the determination of ground and excited state potential energy surfaces of interest in photochemistry. The QM/MM variant of the method, which allows for electrostatic and van der Waals interactions between the QM and MM subsystems, is supplemented with a treatment of covalent interactions based on Antes and Thiels connection atom approach. We concentrate on the correct treatment of electrostatic interactions concerning the connection atom, on the specific requirements for the representation of excited states, and on the transferability of the optimal parameters. We show the viability of the method with four examples of connection atoms: S in a thioether bridge, acylic C, aliphatic C, and N in a peptide. The results obtained with the QM/MM treatment compare well with all-QM results of the same level.     

Are azobenzenophanes rotation-restricted?

We simulated the photoisomerization dynamics of an azobenzenophane with a semiclassical surface hopping approach and a semiempirical reparametrized quantum mechanics/molecular mechanics Hamiltonian. Only one of the two azobenzene chromophores in the molecule is taken into account quantum mechanically: the other one is treated by molecular mechanics. Both n-->pi* and pi-->pi* excitations are considered. Our results show that the photoisomerization reaction mainly involves the rotation around the N=N double bond. The excited state relaxation features are in qualitative agreement with experimental time-resolved fluorescence results.     

Fully three-dimensional accurate modeling of scattering loss in optical waveguides

Scattering loss in high-index-contrast optical waveguides has been modeled by a rigorous 3D numerical algorithm based on volume current method. The electromagnetic field generated by the wire current distribution simulating sidewalls roughness has been calculated by 3D finite element method. The developed modeling technique does not introduce any approximation in radiated power estimation. Numerical results obtained by our model have been compared with some experimental results reported in literature for four typical sub-micrometer high-index-contrast waveguides realized by different technologies and a very good agreement (relative error less than 3%) has been demonstrated. Closed-form expressions for scattering loss in low-index-contrast waveguides have been also derived and discussed. Developed modeling technique has been compared with other three-dimensional algorithms for scattering loss estimation and its advantages in terms of accuracy, computation time and generality have been pointed out. Scattering loss dependence on the parameters of the roughness distribution has been finally discussed.     

Acid character control of bioactive glass/polyvinyl alcohol hybrid foams produced by sol–gel

Bioactive glass/polymer hybrids are promising materials for biomedical applications because they combine the bioactivity of bioceramics with the flexibility of polymers. In previous work hybrid foams with 80% bioactive glass and 20% polyvinyl alcohol were prepared by the sol–gel method. The produced hybrids presented a high acidic character due to the catalysts added. In this work different methods to control the acidity and toxicity of the hybrids were also evaluated, through changes in the synthesis pH and use of different neutralization solutions. The hybrids were prepared with inorganic phase composition of 70%SiO₂–30%CaO and PVA fractions of 20–60% by the sol–gel method. The characterization of the obtained foams was done by FTIR, SEM, Raman Spectroscopy, Helium Picnometry and TGA. The immersion of hybrids in a calcium acetate solution was the most adequate neutralization method. The foams presented porosity of 60–85% and pore diameters of 100–500 μm with interconnected structure.     

Investigation of a point-like and plane-wave excitation in 2D photonic bandgap microcavities using Green’s function method

We report on a new model for simulating wave propagation in two-dimensional photonic crystals (PhCs) by means of Green’s functions rearranged to fit on the geometrical and physical properties of the structure under investigation. The model can take into account physical effects occurring when the PhC is excited by either a point-like source, for the analysis of extended crystals with line and point defects, or a plane wave coming from infinite, to investigate mirrors and microlenses. The model has been used for studying a Fabry–Peròt cavity to evaluate its response in presence of a Hankel source or a plane wave excitation. A parametric investigation of the filter response as a function of the cavity length has been carried out and the best conditions to obtain an increase of quality factor of each resonant cavity mode have been determined.     

Exact analysis of cascaded second-order nonlinearity in rotated Ti:LiNbO3 Couplers

The effects of anisotropic coupling on the nonlinear behavior of different LiNbO₃ waveguides and couplers employing cascaded second-order nonlinearity are analyzed and the importance of leaky mode effect is shown. A set of practical coupling structures made of both symmetric and asymmetric waveguides is investigated and their performance is compared. The home-made computer-code, based on coupled wave theory and anisotropic mode propagation in the complex domain, allows an exact electromagnetic investigation of devices, taking into account both guided and leaky propagation in structures which exhibit losses, the generated second harmonic wave having leaky nature. As an example, for the well-investigated slab three layer waveguide, by taking into account the leaky nature of the generated second harmonic, the modal mismatch = 333 m^–1 is obtained at the azimuthal angle _m 61.9 (between the crystal optical c-axis and the propagation direction) while the angle found via the conventional approach is _m 63.5. Moreover, the calculated second harmonic wave exhibits an attenuation equal to 7.44 × 10^–1dB/cm that strongly influences the whole cascaded second-order phenomenon. The simulation results, for those structures in which it is possible to neglect the hybrid and leaky nature of the propagation modes, are compared with the literature data and an excellent agreement is found.     

Simulation of the photodynamics of azobenzene on its first excited state: comparison of full multiple spawning and surface hopping treatments

We have studied the cis-->trans and trans-->cis photoisomerization of azobenzene after n-->pi* excitation using the full multiple spawning (FMS) method for nonadiabatic wave-packet dynamics with potential-energy surfaces and couplings determined "on the fly" from a reparametrized multiconfigurational semiempirical method. We compare the FMS results with a previous direct dynamics treatment using the same potential-energy surfaces and couplings, but with the nonadiabatic dynamics modeled using a semiclassical surface hopping (SH) method. We concentrate on the dynamical effects that determine the photoisomerization quantum yields, namely, the rate of radiationless electronic relaxation and the character of motion along the reaction coordinate. The quantal and semiclassical results are in good general agreement, confirming our previous analysis of the photodynamics. The SH method slightly overestimates the rate of excited state decay, leading in this case to lower quantum yields.