Search results for "crossing"
showing 10 items of 167 documents
Molecular Basis of DNA Photodimerization: Intrinsic Production of Cyclobutane Cytosine Dimers
2008
Based on CASPT2 results, the present contribution establishes for the first time that cytosine photodimer formation (CC) is mediated along the triplet and singlet manifold by a singlet-triplet crossing, (T1/S0)X, and by a conical intersection, (S1/S0)CI, respectively. The former can be accessed in a barrierless way from a great variety of photochemical avenues and exhibits a covalent single bond between the ethene C6-C6' carbon atoms of each monomer. The efficiency of the stepwise triplet mechanism, however, would be modulated by the effectiveness of the intersystem crossing mechanism. The results provide the grounds for the understanding of the potential photogenotoxicity of endogenous and…
Photostability and Photoreactivity in Biomolecules: Quantum Chemistry of Nucleic Acid Base Monomers and Dimers
2008
The great potentials of high-level ab initio methods, in particular, the CASPT2//CASSCF protocol, are fully illustrated through: (i) the study of ultrafast energy relaxation in DNA/RNA base monomers, (ii) the intrinsic population mechanism of the lowest triplet state, and (iii) how bioexcimers can be considered as precursors of charge transfer and photoinduced reactivity. In order to describe these processes properly, the presence of conical intersections (CIs) and the topology of the involved pathways have to be determined correctly. Thus, in theoretical calculations the dynamic electronic correlation has to be considered. The accessibility of the CIs (or the seam of CIs) becomes crucial t…
Inverse square root level-crossing quantum two-state model
2020
We introduce a new unconditionally solvable level-crossing two-state model given by a constant-amplitude optical field configuration for which the detuning is an inverse-square-root function of time. This is a member of one of the five families of bi-confluent Heun models. We prove that this is the only non-classical exactly solvable field configuration among the bi-confluent Heun classes, solvable in terms of finite sums of the Hermite functions. The general solution of the two-state problem for this model is written in terms of four Hermite functions of a shifted and scaled argument (each of the two fundamental solutions presents an irreducible combination of two Hermite functions). We pr…
Photosensitization and phototherapy with furocoumarins: A quantum-chemical study
2008
Abstract The effect of electromagnetic radiation on biological objects extends from heating to complex photochemistry, and includes DNA alteration, that properly modified in damaged cells may entail beneficial effects. In this regard, psoralen + UV-A (PUVA) therapy, in which furocoumarins, psoralen-like chromophores, are used as photosensitizers and photoreactants with DNA bases, is one of the most promising strategies against a plethora of diseases. Understanding the underlying photochemical mechanisms is crucial to design effective drugs without undesired side effects. We have undertaken a quantum-mechanical study on the photophysics and photochemistry of furocoumarins, analyzing firstly …
Temperature and excitation energy dependence of decay processes of luminescence in Ge-doped silica
2003
We report experimental results on the time decay of photoluminescence at 4.2 eV in Ge-doped silica. This optical emission is assigned to a singlet-singlet transition between electronic states localized on an oxygen deficiency nearby a Ge atom and its radiative decay rate is in competition with an intersystem crossing mechanism that populates an excited triplet state. We investigate the dependence of the lifetime of this photoluminescence on the temperature, in the 6--295 K range, and on the excitation energy, in the ultraviolet and vacuum ultraviolet region. The mean value of the decay time decreases on increasing the temperature, in agreement with the phonon-assisted nature of the intersys…
Exploring two-state reaction pathways in the photodimerization of cyclohexadiene.
2006
The ground- (S0) and lowest triplet-state (T1) pathways associated with dimerization of cyclohexadiene to give [2+2] and [4+2] cycloadducts have been theoretically studied at the UBLYP and UB3LYP levels of theory with the 6-31G* basis set. The DFT energies were validated by CCSD(T) single-point energy calculations. These cycloaddition reactions follow stepwise mechanisms with formation of bis-allylic biradical (BB) intermediates. In the S0 ground state, the interaction between two cyclohexadiene molecules with formation of BB intermediate IN(S0) has a large activation enthalpy of 32.0 kcal mol(-1). On the other hand, C-C bond-formation in the lowest triplet state (T1) leading to BB intermed…
Computational determination of the dominant triplet population mechanism in photoexcited benzophenone
2014
In benzophenone, intersystem crossing occurs efficiently between the S-1(n pi(star)) state and the T-1 state of dominant n pi(star) character, leading to excited triplet states after photoexcitation. The transition mechanism between S-1(n pi(star)) and T-1 is still a matter of debate, despite several experimental studies. Quantum mechanical calculations have been performed in order to assess the relative efficiencies of previously proposed mechanisms, in particular, the direct S-1 -> T-1 and indirect S-1 -> T-2(pi pi(star)) -> T-1 ones. Multiconfigurational wave function based methods are used to discuss the nature of the relevant states and also to determine minimum energy paths a…
Pedestrian Safety Indicators Study
2008
Pedestrian mobility can be considered an important feature in a new model of town organization, being suitable for the newly urbanized areas as well as the old quarters and the outskirts, places where streets and squares, once devised for a pedestrian based mobility, were eventually overcame by an ever increasing motorized traffic. Enhancing pedestrian mobility could bring new life and activities into the old and historic parts of the town reviving their original identities. The last decade’s increase in the recourse to private cars requires improvements in pedestrian mobility quality. This can be achieved by building new infrastructures, limiting the use of private cars, improving public t…
Metabolites of diethylstilboestrol induce sister chromatid exchange in human cultured fibroblasts
1979
Diethylstilboesterol (DES) is one of the few substances for which a clear association with carcinogenicity has been established in man. Nevertheless, it is still widely used, mainly as a cheap oestrogen to increase the slaughter weight of beef, but in spite of this it is not known if residues in the meat or metabolites excreted by the cattle are hazardous to man. It is also unknown whether there is a threshold dose below which DES is harmless. A threshold might be expected if a hormonal mechanism of carcinogensis rather than metabolic activation to an electrophically reactive species operats. This possibility was supported by the observations that DES, in contrast to most other carcinogens,…
Dispersion relation bounds forππscattering
2008
Axiomatic principles such as analyticity, unitarity, and crossing symmetry constrain the second derivative of the $\ensuremath{\pi}\ensuremath{\pi}$ scattering amplitudes in some channels to be positive in a region of the Mandelstam plane. Since this region lies in the domain of validity of chiral perturbation theory, we can use these positivity conditions to bound linear combinations of ${\overline{l}}_{1}$ and ${\overline{l}}_{2}$. We compare our predictions with those derived previously in the literature using similar methods. We compute the one-loop $\ensuremath{\pi}\ensuremath{\pi}$ scattering amplitude in the linear sigma model (LSM) using the $\overline{\mathrm{MS}}$ scheme, a result…