Search results for "Internal conversion"
showing 10 items of 58 documents
Isomeric state of $^{80}$Y and its role in the astrophysical rp-process
2001
5 pages, 7 figures.-- PACS nrs: 21.10.Tg; 23.20.Nx; 27.50.+e.
Polychromatic femtosecond fluorescence studies of metal–polypyridine complexes in solution
2011
Femtosecond-resolved broadband fluorescence studies are reported for[ M(bpy)(3)](2+) (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [ Fe(bpy)(3)](2+) and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the (MLCT)-M-1 fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in <= 30-45 fs due to intersystem crossing to the (MLCT)-M-3 states, but a longer lived component of similar to 190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are character…
Intersystem crossing in Fe(II) coordination compounds
1994
Fe(II) spin-crossover systems can be quantitatively converted from the low-spin (LS) to the high-spin (HS) state well below the thermal transition temperature by irradiating either into the metal-ligand charge transfer or d-d absorption bands, and even in low-spin systems a transient population of the HS state can be achieved. This fact can be made use of to determine HS → LS relaxation rate constants for a wide variety of Fe(II) spin-crossover and low-spin systems. The HS → LS relaxation shows strong deviations from an Arrhenius behaviour, with nearly temperature-independent tunnelling below ∼70 K and a thermally activated process above ∼100 K. The range of more than 12 orders of magnitude…
Excitation of Nucleobases from a Computational Perspective I: Reaction Paths
2013
The main intrinsic photochemical events in nucleobases can be described on theoretical grounds within the realm of non-adiabatic computational photochemistry. From a static standpoint, the photochemical reaction path approach (PRPA), through the computation of the respective minimum energy path (MEP), can be regarded as the most suitable strategy in order to explore the electronically excited isolated nucleobases. Unfortunately, the PRPA does not appear widely in the studies reported in the last decade. The main ultrafast decay observed experimentally for the gas-phase excited nucleobases is related to the computed barrierless MEPs from the bright excited state connecting the initial Franck…
Ab initio modeling of excitonic and charge-transfer states in organic semiconductors: the PTB1/PCBM low band gap system.
2013
A detailed quantum chemical simulation of the excitonic and charge-transfer (CT) states of a bulk heterojunction model containing poly(thieno[3,4-b]thiophene benzodithiophene) (PTB1)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is reported. The largest molecular model contains two stacked PTB1 trimer chains interacting with C60 positioned on top of and lateral to the (PTB1)3 stack. The calculations were performed using the algebraic diagrammatic construction method to second order (ADC(2)). One main result of the calculations is that the CT states are located below the bright inter-chain excitonic state, directly accessible via internal conversion processes. The other important aspects…
Ultrafast decay of the excited singlet states of thioxanthone by internal conversion and intersystem crossing.
2010
The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high-level ab initio CASPT2 calculations of the singlet- and triplet-state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin-orbit coupling terms. The initially populated singlet pi pi* state is shown to decay through internal conversion and intersystem crossing processes via intermediate n pi* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversio…
Monte Carlo simulation of energy absorbed in phenolic ESR dosimeters added with gadolinium exposed to thermal, epithermal and fast neutrons
2017
Abstract In this work analyses of the energy released per unit mass in phenolic compound exposed to neutron beams were performed with the aim of predicting the increase in dose achievable by addition of gadolinium (Gd) inside the pellets. In particular, Monte Carlo (MC) simulations were carried out for IRGANOX® 1076 phenolic compound irradiated with neutron beams with different energy spectra at various depths inside a water phantom. The addition of gadolinium increases sensitivity of phenolic ESR (electron spin resonance) dosimeters to neutrons thanks to the high gadolinium cross section for neutron capture and to the large number of secondary particles (mainly Auger and internal conversio…
Tetrakis{[(p-dodecacarboranyl)methyl]stilbenyl}ethylene: A Luminescent Tetraphenylethylene (TPE) Core System
2017
The synthesis and spectroscopic characterization of the first set of tetra(p-dodecacarborane-stilbeno)ethylenes (TDSE), substituted either with a methyl or phenyl group in the 2-position (Ccluster) of the ortho-carborane, are described. The complex absorption properties are elucidated by TD-DFT calculations, stressing the importance of through bond conjugation. Enhanced conjugation and restriction of the conformational space are identified as the main factors for boosted luminescence properties in solution compared to tetraphenylethylene (TPE) core, effectively reducing internal conversion (IC). IC is further reduced when aggregate suspensions of our compounds in water are formed, providing…
Ultrafast internal conversion of excited cytosine via the lowest pipi electronic singlet state.
2003
Computational evidence at the CASPT2 level supports that the lowest excited state pipi* contributes to the S1/S0 crossing responsible for the ultrafast decay of singlet excited cytosine. The computed radiative lifetime, 33 ns, is consistent with the experimentally derived value, 40 ns. The nOpi* state does not play a direct role in the rapid repopulation of the ground state; it is involved in a S2/S1 crossing. Alternative mechanisms through excited states pisigma* or nNpi* are not competitive in cytosine.
Are the five natural DNA/RNA base monomers a good choice from natural selection?
2009
In order to prevent the damaging effects of sun radiation in the genetic material, its constituent chromophores, the five natural DNA/RNA nucleobases cytosine, thymine, uracil, adenine, and guanine, should be able to efficiently dissipate absorbed radiation, UV specifically, avoiding as much as possible photoreactions leading to lesions. It has been established experimentally and theoretically that efficient internal conversion channels, still open and relevant in the oligomer-stacked strands, exist in the monomers allowing an effective waste of the initial energy. Previous evidences cannot explain, however, why minor differences in the molecular structure modify drastically the photochemis…