Femtosecond dynamics of DNA-mediated electron transfer

Diverse biophysical and biochemical studies have sought to understand electron transfer (ET) in DNA in part because of its importance to DNA damage and its repair. However, the dynamics and mechanisms of the elementary processes of ET in this medium are not fully understood and have been heavily debated. Two fundamental issues are the distance over which charge is transported and the time-scale on which the transport through the π-stack of the DNA base pairs may occur. With femtosecond resolution, we report direct observation in DNA of ultrafast ET, initiated by excitation of tethered ethidium (E), the intercalated electron acceptor (A); the electron donor (D) is 7-deazaguanine (Z), a modified base, placed at different, fixed distances from A. The ultrafast ET between these reactants in DNA has been observed with time constants of 5 ps and 75 ps and was found to be essentially independent of the D–A separation (10–17 Å). However, the ET efficiency does depend on the D–A distance. The 5-ps decay corresponds to direct ET observed from 7-deazaguanine but not guanine to E. From measurements of orientation anisotropies, we conclude that the slower 75-ps process requires the reorientation of E before ET, similar to E/nucleotide complexes in water. These results reveal the nature of ultrafast ET and its mechanism: in DNA, ET cannot be described as in proteins simply by a phenomenological parameter, β. Instead, the involvement of the base pairs controls the time scale and the degree of coherent transport.

Intermolecular and Intramolecular Charge Transfer in Functional Molecular Materials

This thesis is devoted to the investigation of inter and intramolecular charge transfer (CT) in molecular functional materials and specifically organic dyes and CT crystals. An integrated approach encompassing quantum-chemical calculations, semiempirical tools, theoretical models and spectroscopic measurements is applied to understand structure-property relationships governing the low-energy physics of these materials. Four main topics were addressed: 1) Spectral properties of organic dyes. Charge-transfer dyes are constituted by electron donor (D) and electron acceptor (A) units linked through bridge(s) to form molecules with different symmetry and dimensionality. Their low-energy physics is governed by the charge resonance between D and A groups and is effectively described by a family of parametric Hamiltonians known as essential-state models. These models account for few electronic states, corresponding to the main resonance structures of the relevant dye, leading to a simple picture that is completed introducing the coupling of the electronic system to molecular vibrations, treated in a non-adiabatic way, and an effective classical coordinate, describing polar solvation. In this work a specific essential-state model was proposed and parametrized for the dye Brilliant Green. The central issue in this work has been the definition of the diabatic states, a not trivial task for a multi-branched chromophore. In a second effort, we have used essential-state models for the description of the early-stage dynamics of excited states after ultrafast excitation. Crucial to this work is the fully non-adiabatic treatment of the coupled electronic and vibrational motion, allowing for a reliable description of the dynamics of systems showing a multistable, broken-symmetry excited state. 2) Mixed-stack CT salts. Mixed-stack (MS) CT crystals are an interesting class of multifunctional molecular materials, where D and A molecules arrange themselves to form stacks, leading to delocalized electrons in one dimension. The interplay between the intermolecular CT, electrostatic interactions, lattice phonons and molecular vibrations leads to intriguing physical properties that include (photoinduced) phase transitions, multistability, antiferromagnetism, ferroelectricity and potential multiferroicity. The standard microscopic model to describe this family of materials is the Modified Hubbard model accounting for electron-phonon coupling (Peierls coupling), electron-molecular vibrations coupling (Holstein coupling) and electrostatic interactions. We adopt and validate a method, based on DFT calculations on dimeric DA structures, to extract relevant model parameters. The approach offers a powerful tool to shed light on the complex physics of MS-CT salts. 3) Charge transfer in organic radical dipolar dyes. In collaboration with the group of Prof. Jaume Veciana (ICMAB- Barcellona), we have studied spectral properties of a special class of CT dyes with D-bridge-A structure where the acceptor group is a stable radical (of the perchlorotriphenylmethyl, PTM, family), leading to an open-shell CT dyes. These materials are of interest since they associate the electronic and optical properties of CT dyes with magnetic properties from the unpaired electron. The first effort was devoted to the parametrization of the relevant essential-state model. Two strategies were adopted, one based on the calculation of the low-energy spectral properties, the other based on the variation of ground state properties with an applied electric field. 4) The spectral properties of organic nanoparticles based on radical species are investigated in collaboration with Dr. I. Ratera (ICMAB- Barcellona). Intriguing spectroscopic behavior was observed pointing to the presence of excimer states. In an attempt to rationalize these findings, extensive calculations (TD-DFT and ZINDO) were performed. The results for the isolated dyes are validated against experimental spectra in solution. To address intermolecular interactions we studied dimeric structures in the gas phase, but the preliminary results obtained do not support excimer formation.

Polarized interacting exciton gas in quantum wells and bulk semiconductors

We develop a theory to calculate exciton binding energies of both two- and three-dimensional spin polarized exciton gases within a mean field approach. Our method allows the analysis of recent experiments showing the importance of the polarization and intensity of the excitation light on the exciton luminescence of GaAs quantum wells. We study the breaking of the spin degeneracy observed at high exciton density (5×1010 cm2). Energy level splitting between spin +1 and spin -1 is shown to be due to many-body interexcitonic exchange while the spin relaxation time is controlled by intraexciton exchange. © 1996 The American Physical Society.

Spin splitting in a polarized quasi-two-dimensional exciton gas

We have observed a large spin splitting between "spin" +1 and -1 heavy-hole excitons, having unbalanced populations, in undoped GaAs/AlAs quantum wells in the absence of any external magnetic field. Time-resolved photoluminescence spectroscopy, under excitation with circularly polarized light, reveals that, for high excitonic density and short times after the pulsed excitation, the emission from majority excitons lies above that of minority ones. The amount of the splitting, which can be as large as 50% of the binding energy, increases with excitonic density and presents a time evolution closely connected with the degree of polarization of the luminescence. Our results are interpreted on the light of a recently developed model, which shows that, while intraexcitonic exchange interaction is responsible for the spin relaxation processes, exciton-exciton interaction produces a breaking of the spin degeneracy in two-dimensional semiconductors.

Exact and analytic-numerical solutions of lagging models of heat transfer in a semi-infinite medium

Different non-Fourier models of heat conduction have been considered in recent years, in a growing area of applications, to model microscale and ultrafast, transient, nonequilibrium responses in heat and mass transfer. In this work, using Fourier transforms, we obtain exact solutions for different lagging models of heat conduction in a semi-infinite domain, which allow the construction of analytic-numerical solutions with prescribed accuracy. Examples of numerical computations, comparing the properties of the models considered, are presented.

Ultrashort pulse generation from diode laser devices

This thesis presents a detailed, experiment-based study of generation of ultrashort optical pulses from diode lasers. Simple and cost-effective techniques were used to generate high power, high quality optical short pulses at various wavelength windows. The major achievements presented in the thesis is summarised as follows. High power pulses generation is one of the major topics discussed in the thesis. Although gain switching is the simplest way for ultrashort pulse generation, it proves to be quite effective to deliver high energy pulses on condition that the pumping pulses with extremely fast rising time and high enough amplitude are applied on specially designed pulse generators. In the experiment on a grating-coupled surface emitting laser (GCSEL), peak power as high as 1W was achieved even when its spectral bandwidth was controlled within 0.2nm. Another experiment shows violet picosecond pulses with peak power as high as 7W was achieved when the intensive electrical pulses were applied on optimised DC bias to pump on InGaN violet diode laser. The physical mechanism of this phenomenon, as we considered, may attributed to the self-organised quantum dots structure in the laser. Control of pulse quality, including spectral quality and temporal profile, is an important issue for high power pulse generation. The ways to control pulse quality described in the thesis are also based on simple and effective techniques. For instance, GCSEL used in our experiment has a specially designed air-grating structure for out-coupling of optical signals; hence, a tiny flat aluminium mirror was placed closed to the grating section and resulted in a wavelength tuning range over 100nm and the best side band suppression ratio of 40dB. Self-seeding, as an effective technique for spectral control of pulsed lasers, was demonstrated for the first time in a violet diode laser. In addition, control of temporal profile of the pulse is demonstrated in an overdriven DFB laser. Wavelength tuneable fibre Bragg gratings were used to tailor the huge energy tail of the high power pulse. The whole system was compact and robust. The ultimate purpose of our study is to design a new family of compact ultrafast diode lasers. Some practical ideas of laser design based on gain-switched and Q-switched devices are also provided in the end.

Switching and generation of ultrashort pulses using all-fibre devices

Serial and parallel interconnection of photonic devices is integral to the construction of any all-optical data processing system. This thesis presents results from a series of experiments centering on the use of the nonlinear-optical loop mirror (NOLM) switch in architectures for the manipulation and generation of ultrashort pulses. Detailed analysis of soliton switching in a single NOLM and cascade of two NOLM's is performed, centering on primary limitations to device operation, effect of cascading on amplitude response, and impact of switching on the characteristics of incident pulses. By using relatively long input pulses, device failure due to stimulated Raman generation is postponed to demonstrate multiple-peaked switching for the first time. It is found that while cascading leads to a sharpening of the overall switching characteristic, pulse spectral and temporal integrity is not significantly degraded, and emerging pulses retain their essential soliton character. In addition, by including an asymmetrically placed in-fibre Bragg reflector as a wavelength selective loss element in the basic NOLM configuration, both soliton self-switching and dual-wavelength control-pulse switching are spectrally quantised. Results are presented from a novel dual-wavelength laser configuration generating pulse trains with an ultra-low rms inter-pulse-stream timing jitter level of 630fs enabling application in ultrafast switching environments at data rates as high as 130GBits/s. In addition, the fibre NOLM is included in architectures for all-optical memory, demonstrating storage and logical inversion of a 0.5kByte random data sequence; and ultrafast phase-locking of a gain-switched distributed feedback laser at 1.062GHz, the fourteenth harmonic of the system baseband frequency. The stringent requirements for environmental robustness of these architectures highlight the primary weaknesses of the NOLM in its fibre form and recommendations to overcome its inherent drawbacks are presented.

3D Reconstruction of the complex dielectric function of glass during femtosecond laser micro-fabrication

We report on a new technique to reconstruct the 3D dielectric function change in transparent dielectric materials and the application of the technique for on-line monitoring of refractive index modification in BK7 glass during direct femtosecond laser microfabrication. The complex optical field scattered from the modified region is measured using two-beam, single-shot interferogram and the distribution of the modified refractive index is reconstructed by numerically solving the inverse scattering problem in Born approximation. The optical configuration suggested is further development of digital holographic microscopy (DHM). It takes advantage of high spatial resolution and almost the same optical paths for both interfering beams, and allows ultrafast time resolution.

Mask-less lithography for fabrication of optical waveguides

A flexible method for fabricating shallow optical waveguides by using femtosecond laser writing of patterns on a metal coated glass substrate followed by ion-exchange is described. This overcomes the drawbacks of low index contrast and high induced stress in waveguides directly written using low-repetition rate ultrafast laser systems. When compared to conventional lithography, the technique is simpler and has advantages in terms of flexibility in the types of structures which can be fabricated.

Mask-less lithography for fabrication of optical waveguides

A flexible method for fabricating shallow optical waveguides by using femtosecond laser writing of patterns on a metal coated glass substrate followed by ion-exchange is described. This overcomes the drawbacks of low index contrast and high induced stress in waveguides directly written using low-repetition rate ultrafast laser systems. When compared to conventional lithography, the technique is simpler and has advantages in terms of flexibility in the types of structures which can be fabricated.

3D reconstruction of the complex dielectric function of glass during femtosecond laser micro-fabrication

We report on a new technique to reconstruct the 3D dielectric function change in transparent dielectric materials and the application of the technique for on-line monitoring of refractive index modification in BK7 glass during direct femtosecond laser microfabrication. The complex optical field scattered from the modified region is measured using two-beam, single-shot interferogram and the distribution of the modified refractive index is reconstructed by numerically solving the inverse scattering problem in Born approximation. The optical configuration suggested is further development of digital holographic microscopy. It takes advantage of high spatial resolution and almost the same optical paths for both interfering beams, and allows ultrafast time resolution. © Springer Science+Business Media, LLC. 2011.

Waveguide fabrication in lithium-niobo-phosphate glasses by high repetition rate femtosecond laser:route to non-equilibrium material’s states

We study waveguide fabrication in lithium-niobo-phosphate glass, aiming at a practical method of single-stage fabrication of nonlinear integrated-optics devices. We observed chemical transformations or material redistribution during the course of high repetition rate femtosecond laser inscription. We believe that the laser-induced ultrafast heating and cooling followed by elements diffusion on a microscopic scale opens the way toward the engineering non-equilibrium sates of matter and thus can further enhance Refractive Index (RI) contrasts by virtue of changing glass composition in and around the fs tracks. © 2014 Optical Society of America.

THz emission from quantum dot-based THz antennas pumped by a tunable quantum-dot laser diode

The THz optoelectronics field is now maturing and semiconductor-based THz antenna devices are becoming more widely implemented as analytical tools in spectroscopy and imaging. Photoconductive (PC) THz switches/antennas are driven optically typically using either an ultrashort-pulse laser or an optical signal composed of two simultaneous longitudinal wavelengths which are beat together in the PC material at a THz difference frequency. This allows the generation of (photo)carrier pairs which are then captured over ultrashort timescales usually by defects and trapping sites throughout the active material lattice. Defect-implanted PC materials with relatively high bandgap energy are typically used and many parameters such as carrier mobility and PC gain are greatly compromised. This paper demonstrates the implementation of low bandgap energy InAs quantum dots (QDs) embedded in standard crystalline GaAs as both the PC medium and the ultrafast capture mechanism in a PC THz antenna. This semiconductor structure is grown using standard MBE methods and allows the device to be optically driven efficiently at wavelengths up to ~1.3 µm, in this case by a single tunable dual-mode QD diode laser.