Search results for "Triplet"
showing 10 items of 159 documents
Computer Modeling of Luminescence in ABO3 Perovskites
2001
ABSTRACTWe suggest theoretical interpretation to a long-debated discussion on a nature of the intrinsic “green” luminescence observed in many ABO3 perovskites. For this purpose we performed quantum chemical calculations using the Intermediate Neglect of the Differential Overlap combined with the Large Unit Cell periodic model. Triplet exciton which is very likely responsible for the “green” luminescence is shown to be in a good approximation a pair of nearest Jahn-Teller electron and hole polarons (a bipolaron).
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 …
Structure sensitive investigations on luminescence centres in Mn-activated LiBaF3 dosimeters
2008
Abstract Prior to x-irradiation the photoluminescence (PL) of Mn-activated LiBaF3 shows a Mn 2 + emission band at 710 nm; the corresponding excitation bands are between 210 and 620 nm. After x-irradiation the PL emission spectrum shows a band peaking at about 610 nm which is tentatively assigned to a perturbed Mn 2 + emission; the intensity of all PL emission bands is increased. Structure sensitive investigations on the radiation-induced emission band were done by detecting electron paramagnetic resonance (EPR) induced changes in the integral PL emission at a temperature of 1.5 K. The analysis of the angular dependent PL-EPR spectra, recorded for different orientations of the magnetic field…
Self-trapped exciton in Li2GeO3
1997
Abstract Self-trapped excitons (STE) are discovered in Li2GeO3 crystal. The PL band at 2.7 eV with a strong Stoke's shift is excited in the intrinsic absorption range of Li2GeO3 crystal, in which the optical gap is situated at 6 eV. The activation energy of the STE luminescence thermal quenching is not monoenergetic and is situated in the range 40–100 meV. The luminescence is strongly polarized. The decay kinetics can be characterized by τ = 0.9 ms at 45 K. At 5 K it can be approximated by fast (0.6 ms) and slow (4–2.5 ms) components. Decay kinetics is determined by triplet state of STE splits in zero magnetic field. Two different excited triplet states (centers) have the average ODMR param…
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…
Design of carborane molecular architectures with electronic structure computations: From endohedral and polyradical systems to multidimensional netwo…
2009
11 pags, 6 figs. -- 19th International Conference on Physical Organic Chemistry (ICPOC-19) 13–18 July 2008, Santiago de Compostela, Spain
Spin-Based Quantum Information Processing in Magnetic Quantum Dots
2005
We define the qubit as a pair of singlet and triplet states of two electrons in a He-type quantum dot (QD) placed in a diluted magnetic semiconductor (DMS) medium. The molecular field is here essential as it removes the degeneracy of the triplet state and strongly enhances the Zeeman splitting. Methods of qubit rotation as well as two-qubit operations are suggested. The system of a QD in a DMS is described in a way which allows an analysis of the decoherence due to spin waves in the DMS subsystem.
Synthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]−: structural diversity in lithium(i), zinc(ii) and nickel(ii) complexes
2016
A high-yield synthesis of [Li{S(H)C(PPh2S)2}]2 [Li2·(3)2] was developed and this reagent was used in metathesis with ZnCl2 and NiCl2 to produce homoleptic complexes 4 and 5b in 85 and 93% yields, respectively. The solid-state structure of the octahedral complex [Zn{S(H)C(PPh2S)2}2] (4) reveals notable inequivalence between the Zn-S(C) and Zn-S(P) contacts (2.274(1) Å vs. 2.842(1) and 2.884(1) Å, respectively). Two structural isomers of the homoleptic complex [Ni{S(H)C(PPh2S)2}2] were isolated after prolonged crystallization processes. The octahedral green Ni(ii) isomer 5a exhibits the two monoprotonated ligands bonded in a tridentate (S,S',S'') mode to the Ni(ii) centre with three distinctl…
Characterization of a sucrose/starch matrix through positron annihilation lifetime spectroscopy: unravelling the decomposition and glass transition p…
2010
The triplet state of positronium, o-Ps, is used as a probe to characterize a starch-20% w/w sucrose matrix as a function of temperature (T). A two-step decomposition (of sucrose, and then starch) starts at 440 K as shown by a decrease in the o-Ps intensity (I(3)) and lifetime (τ(3)), the latter also disclosing the occurrence of a glass transition. Upon sucrose decomposition, the matrix acquires properties (reduced size and density of nanoholes) that are different from those of pure starch. A model is successfully established, describing the variations of both I(3) and τ(3) with T and yields a glass transition temperature, T(g) = (446 ± 2) K, in spite of the concomitant sucrose decomposition…