Electron Localization Dynamics in the Triplet Excited State of [Ru(bpy)3]2+ in Aqueous Solution

Hybrid DFT/classical molecular dynamics of the long‐lived triplet excited state of [Ru(bpy)₃]²⁺ (bpy=2,2′‐bipyridine) in aqueous solution is used to investigate the solvent‐mediated electron localization and dynamics in the triplet metal‐to‐ligand charge‐transfer (MLCT) state. Our studies reveal a solvent‐induced breaking of the coordination symmetry with consequent localization of the photoexcited electron on one or two bipyridine units for the entire length of our simulation, which amounts to several picoseconds. Frequent electronic “hops” between the ligands constituting the pair are observed with a characteristic time of approximately half a picosecond.     

Comparative morphology of early stages of two Mediterranean Sarcophaga Meigen, 1826 (Diptera; Sarcophagidae) and a review of the feeding habits of Palaearctic species

The third instar larva of Sarcophaga hirticrus Pandellé, 1896 and Sarcophaga javita (Peris, González-Mora and Mingo, 1998) are described and figured for the first. The use of scanning electron microscopy (SEM) has been demonstrated as an effective tool for determining differences at the specific level, and is here applied. The two species are distinguished from other Sarcophaga spp. and the principal diagnostic character states are illustrated and discussed. Comparative information on immature stages morphology of the described Palaearctic Sarcophaga species and its feeding habits are compiled and provided in a tabulated form.     

Photon echo peak shift experiments in the UV: p-terphenyl in different solvents

In this article we present a new photon echo set-up operating in the UV range and our first results of photon echo peak shift (PEPS) experiments of a small non-polar dye molecule, p-terphenyl (pTP), in three different solvents: ethanol, methanol and 2-propanol. The experiments show the feasibility of UV transient grating and photon echo measurements and highlight the sensitivity of this technique for the study of non-polar solvation dynamics. The transient grating experiments indicate a relaxation of the ground state hole of about 6 ps. The photon echo experiments show that while electronic dephasing occurs on timescales shorter than 100 fs, solvation dynamics timescales are in the picosecond regime, in agreement with the literature.     

A new band system in the ultraviolet emission spectrum of no trapped in an argon matrix

A new ultraviolet band system identified as emission from the theoretically predicted but so far unobserved ²Φ state of NO trapped in an argon matrix is reported. The energy of the ν = 0 level is estimated to be 6.57 ± 0.015 or 6.785 ± 0.015 eV. The intensity distribution yields an internuclear distance of 1.415 ± 0.015 Å.     

Structural determination of a short-lived excited iron(II) complex by picosecond x-ray absorption spectroscopy

Structural changes of the iron(II)-tris-bipyridine ([Fe(II)(bpy)(3)](2+)) complex induced by ultrashort pulse excitation and population of its short-lived (< or =0.6 ns) quintet high spin state have been detected by picosecond x-ray absorption spectroscopy. The structural relaxation from the high spin to the low spin state was followed over the entire lifetime of the excited state. A combined analysis of the x-ray-absorption near-edge structure and extended x-ray-absorption fine structure spectroscopy features delivers an Fe-N bond elongation of 0.2 A in the quintet state compared to the singlet ground state.     

Femtosecond fluorescence upconversion setup with broadband detection in the ultraviolet

We show a femtosecond fluorescence upconversion setup with broadband detection to measure time-resolved emission spectra in the 300-550 nm range, upon excitation between 250 and 300 nm, with a time resolution of 100 fs. We present time-resolved fluorescence emission spectra of 2,5-diphenyloxazole in solution, which demonstrate the capabilities of the setup.     

CNDOL: A fast and reliable method for the calculation of electronic properties of very large systems. Applications to retinal binding pocket in rhodopsin and gas phase porphine

Very large molecular systems can be calculated with the so called CNDOL approximate Hamiltonians that have been developed by avoiding oversimplifications and only using a priori parameters and formulas from the simpler NDO methods. A new diagonal monoelectronic term named CNDOL/21 shows great consistency and easier SCF convergence when used together with an appropriate function for charge repulsion energies that is derived from traditional formulas. It is possible to obtain a priori molecular orbitals and electron excitation properties after the configuration interaction of single excited determinants with reliability, maintaining interpretative possibilities even being a simplified Hamiltonian. Tests with some unequivocal gas phase maxima of simple molecules (benzene, furfural, acetaldehyde, hexyl alcohol, methyl amine, 2,5 dimethyl 2,4 hexadiene, and ethyl sulfide) ratify the general quality of this approach in comparison with other methods. The calculation of large systems as porphine in gas phase and a model of the complete retinal binding pocket in rhodopsin with 622 basis functions on 280 atoms at the quantum mechanical level show reliability leading to a resulting first allowed transition in 483 nm, very similar to the known experimental value of 500 nm of "dark state." In this very important case, our model gives a central role in this excitation to a charge transfer from the neighboring Glu(-) counterion to the retinaldehyde polyene chain. Tests with gas phase maxima of some important molecules corroborate the reliability of CNDOL/2 Hamiltonians.     

Semi-Parametric Estimation Using Bernstein Polynomial and a Finite Gaussian Mixture Model

The central focus of this paper is upon the alleviation of the boundary problem when the probability density function has a bounded support. Mixtures of beta densities have led to different methods of density estimation for data assumed to have compact support. Among these methods, we mention Bernstein polynomials which leads to an improvement of edge properties for the density function estimator. In this paper, we set forward a shrinkage method using the Bernstein polynomial and a finite Gaussian mixture model to construct a semi-parametric density estimator, which improves the approximation at the edges. Some asymptotic properties of the proposed approach are investigated, such as its probability convergence and its asymptotic normality. In order to evaluate the performance of the proposed estimator, a simulation study and some real data sets were carried out.     

Exciton decay mechanism in DNA single strands: back-electron transfer and ultrafast base motions

The photochemistry of DNA systems is characterized by the ultraviolet (UV) absorption of π-stacked nucleobases, resulting in exciton states delocalized over several bases. As their relaxation sensitively depends on local stacking conformations, disentangling the ensuing electronic and structural dynamics has remained an experimental challenge, despite their fundamental role in protecting the genome from potentially harmful UV radiation. Here we use transient absorption and transient absorption anisotropy spectroscopy with broadband femtosecond deep-UV pulses (250–360 nm) to resolve the exciton dynamics of UV-excited adenosine single strands under physiological conditions. Due to the exceptional deep-UV bandwidth and polarization sensitivity of our experimental approach, we simultaneously resolve the population dynamics, charge-transfer (CT) character and conformational changes encoded in the UV transition dipoles of the π-stacked nucleotides. Whilst UV excitation forms fully charge-separated CT excitons in less than 0.3 ps, we find that most decay back to the ground state via a back-electron transfer. Based on the anisotropy measurements, we propose that this mechanism is accompanied by a structural relaxation of the photoexcited base-stack, involving an inter-base rotation of the nucleotides. Our results finally complete the exciton relaxation mechanism for adenosine single strands and offer a direct view into the coupling of electronic and structural dynamics in aggregated photochemical systems.

Despite its key role in DNA photochemistry, the decay mechanism of excitons in stacked bases has remained difficult to resolve. Ultrafast polarization spectroscopy now reveals a back-electron transfer and ultrafast base motions in adenosine strands.