Conical intersections in thymine

The mechanisms which are responsible for the radiationless deactivation of the npi* and pipi* excited singlet states of thymine have been investigated with multireference ab initio methods (the complete-active-space self-consistent-field (CASSCF) method and second-order perturbation theory with respect to the CASSCF reference (CASPT2)) as well as with the CC2 (approximated singles and doubles coupled-cluster) method. The vertical excitation energies, the equilibrium geometries of the 1npi*and 1pipi* states, as well as their adiabatic excitation energies have been determined. Three conical intersections of the S1 and S0 energy surfaces have been located. The energy profiles of the excited states and the ground state have been calculated with the CASSCF method along straight-line reaction paths leading from the ground-state equilibrium geometry to the conical intersections. All three conical intersections are characterized by strongly out-of-plane distorted geometries. The lowest-energy conical intersection (CI1) arises from a crossing of the lowest 1pipi* state with the electronic ground state. It is found to be accessible in a barrierless manner from the minimum of the 1pipi* state, providing a direct and fast pathway for the quenching of the population of the lowest optically allowed excited states of thymine. This result explains the complete diffuseness of the absorption spectrum of thymine in supersonic jets. The lowest vibronic levels of the optically nearly dark 1npi* state are predicted to lie below CI1, explaining the experimental observation of a long-lived population of dark excited states in gas-phase thymine.     

Diffusion of dextran within poly(methacrylic acid) hydrogels

We describe an investigation of fluorescence correlation spectroscopy into the diffusion of fluorescein‐tagged dextran (FDEX) in a poly(methacrylic acid) (PMAA) hydrogel. The temperature dependence of FDEX diffusion is shown to follow Zimm behavior in pure water, and the decrease in the diffusion coefficient when in the PMAA hydrogel has been modeled. The addition of acid and alkali (HCl and NaOH, respectively) not only control the swelling and collapse of the hydrogel but also reveal a strong pH dependence of the dextran diffusion coefficient, which shows a (nonmonatonic) increase with pH. The addition of NaCl and CaCl₂ salts similarly showed evidence of network swelling, most notably at low salt concentration, but also that the diffusion coefficient within the gel at these low concentrations is larger than that in the equivalent solution without the hydrogel, indicating that the combination of hydrogel and salt works to increase the diffusion coefficient above that in pure water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Photoinduced electron and proton transfer in the hydrogen-bonded pyridine-pyrrole system

We present here a detailed analysis of the mechanism of photoinduced electron and proton transfer in the planar pyrrole-pyridine hydrogen-bonded system, a model for the photochemistry of hydrogen bonds in DNA base pairs. Two different crossings, an avoided crossing and a conical intersection, are the key steps for forward and backward electron and proton transfer providing to the system photostability against UV radiation by restoring the system in its initial electronic and geometric structure.     

Glycine in an electronically excited state: ab initio electronic structure and dynamical calculations

The goal of this study is to explore the photochemical processes following optical excitation of the glycine molecule into its two low-lying excited states. We employed electronic structure methods at various levels to map the PES of the ground state and the two low-lying excited states of glycine. It follows from our calculations that the photochemistry of glycine can be regarded as a combination of photochemical behavior of amines and carboxylic acid. The first channel (connected to the presence of amino group) results in ultrafast decay, while the channels characteristic for the carboxylic group occur on a longer time scale. Dynamical calculations provided the branching ratio for these channels. We also addressed the question whether conformationally dependent photochemistry can be observed for glycine. While electronic structure calculations favor this possibility, the ab initio multiple spawning (AIMS) calculations showed only minor relevance of the reaction path resulting in conformationally dependent dynamics.     

Computational studies of aqueous-phase photochemistry and the hydrated electron in finite-size clusters

A survey of recent ab initio calculations on excited electronic states of water clusters and various chromophore-water clusters is given. Electron and proton transfer processes in these systems have been characterized by the determination of electronic wave functions, minimum-energy reaction paths and potential-energy profiles. It is pointed out that the transfer of a neutral hydrogen atom (leading to biradicals) rather than the transfer of a proton (leading to ion pairs) is the generic excited-state reaction mechanism in these systems. The hydrated hydronium radical, (H3O)(aq), plays a central role in this scenario. The electronic and vibrational spectra of H3O(H2O)(n) clusters and the decay mechanism of these metastable species have been investigated in some detail. The results suggest that (H3O)(aq) could be the carrier of the characteristic spectroscopic properties of the hydrated electron in liquid water.     

Electrical characteristics of argon radio frequency glow dischargesin an asymmetric cell

Measurements of the current and voltage at both electrodes of a parallel-plate, capacitively coupled RF discharge cell (the Gaseous Electronics Conference Reference Cell) were combined with measurements of the voltage on a wire inserted into the glow region between the electrodes, for argon discharges at pressures of 1.3-133 Pa and peak-to-peak applied voltages ⩽400 V. Together, these measurements determined the RF voltage, current, impedance, and power of each sheath of the plasma. Simple power laws were found to describe changes in sheath impedances observed as voltage and pressure were varied. An equivalent circuit model for the electrical behavior of the discharge was obtained. The equivalent circuit model can be used to relate the electrical data to plasma properties such as electron densities, ion currents, and sheath widths. The results differ from models previously proposed for asymmetric RF discharges, and the implications of this disagreement are discussed     

Recent trends in ultra‐fast HPLC: New generation superficially porous silica columns

New generation columns, i.e. packed with superficially porous silica particles are available as trade names with following manufacturers: Halo, Ascentis Express, Proshell 120, Kinetex, Accucore, Sunshell, and Nucleoshell. These provide ultra‐fast HPLC separations for a variety of compounds with moderate sample loading capacity and low back pressure. Chemistries of these columns are C₈, C₁₈, RP‐Amide, hydrophilic interaction liquid chromatography, penta fluorophenyl (PFP), F5, and RP‐aqua. Normally, the silica gel particles are of 2.7 and 1.7 μm as total and inner solid core diameters, respectively, with 0.5‐μm‐thick of outer porous layer having 90 Å pore sizes and 150 m²/g surface area. This article describes these new generation columns with special emphasis on their textures and chemistries, separations, optimization, and comparison (inter and intra stationary phases). Besides, future perspectives have also been discussed.     

Photophysics of indole-2-carboxylic acid in an aqueous environment studied by fluorescence spectroscopy in combination with ab initio calculations

The photo-physics and -chemistry of indoles are known to be highly complex and strongly dependent on their precise molecular structure and environment. Combination of spectroscopic analysis with quantum chemical calculations should be a powerful tool to unravel precise excited state deactivation mechanisms. At the same time, combined studies are seldom and likely far from trivial. In this work we explore the feasibility of combining spectroscopic and quantum-chemical data into one consistent model. The molecule of choice is indole-2-carboxylic acid (ICA) in aqueous media. Excited state dynamics are determined by time-resolved fluorescence experiments, while excited state reaction pathways of ICA-H(2)O clusters are explored by ab initio calculations.     

Generation of THz transients by photoexcited single-crystal GaAs meso-structures

We report a sub-picosecond photoresponse and THz transient generation of GaAs single-crystal mesoscopic platelets excited by femtosecond optical pulses. Our structures were fabricated by a top-down technique, by patterning an epitaxial, 500-nm-thick GaAs film grown on top of an AlAs sacrificial layer and then transferring the resulting etched away 10 × 20-μm² platelets onto an MgO substrate using a micropipette. The freestanding GaAs devices, incorporated into an Au coplanar strip line, exhibited extremely low dark currents and ~0.4 % detection efficiency at 10 V bias. The all-optical, pump–probe carrier dynamics analysis showed that, for 800-nm-wavelength excitation, the intrinsic relaxation of photocarriers featured a 310-fs-wide transient with a 290 fs fall time. We have also carried out a femtosecond, time-resolved electro-optic characterization of our devices and recorded along the transmission line the electrical transients as short as ~600 fs, when the platelet was excited by a train of 100-fs-wide, 800-nm-wavelength optical laser pulses. The platelets have been also demonstrated to be very efficient generators of free-space propagating THz transients with the spectral bandwidth exceeding 2 THz. The presented performance of the epitaxial, freestanding GaAs meso-structured photodevices makes them uniquely suitable for THz-frequency optoelectronic applications, ranging from ultrafast photodetectors to THz-bandwidth optical-to-electrical transducers and photomixers.