Search results for "SINGLET"
showing 10 items of 352 documents
Conformational disorder and optical properties of point defects in vitreous silica
2004
Abstract Disordered systems are characterized by the presence of local conformational heterogeneity, which reflects the complex landscape of the potential energy of the vitreous state. Optical properties of defects embedded in a vitreous matrix are also determined by the interaction with the surrounding environment; so the conformational disorder of the system induces spectral inhomogeneity. As a consequence, detailed experimental investigation of absorption and photoluminescence bands can give information on configurational substates around the chromophore. We focused our attention on B-type optical activity in silica glasses, characterized by a singlet emission and a triplet emission, conne…
Temperature dependence of O2 singlet photoluminescence in silica nanoparticles
2013
Abstract The near infrared singlet emission and photoluminescence lifetime of O 2 molecules embedded in silica nanoparticles are studied from room temperature down to 10 K. The area of the photoluminescence band under infrared excitation decreases for temperature above 100 K and the lifetime is shortened. These observations provide evidence of a thermally activated relaxation channel with activation energy of about 40 meV. This relaxation mechanism adds to the already known temperature independent electronic-to-vibrational coupling involving high energy vibrational modes of the host matrix or its impurities. The thermally activated process is suggested to consist in the breakage of the O 2 …
Modification of Structural and Luminescence Properties of Graphene Quantum Dots by Gamma Irradiation and Their Application in a Photodynamic Therapy
2015
Herein, the ability of gamma irradiation to enhance the photoluminescence properties of graphene quantum dots (GQDs) was investigated. Different doses of gamma-irradiation were used on GQDs to examine the way in which their structure and optical properties can be affected. The photoluminescence quantum yield was increased six times for the GQDs irradiated with high doses compared to the nonirradiated material. Both photoluminescence lifetime and values of optical band gap were increased with the dose of applied gamma irradiation. In addition, the exploitation of the gamma-irradiated GQDs as photosensitizers was examined by monitoring the production of singlet oxygen under UV illumination. T…
Photoluminescence spectral dispersion as a probe of structural inhomogeneity in silica
2011
We perform time-resolved photoluminescence measurements on point defects in amorphous silicon dioxide (silica). In particular, we report data on the decay kinetics of the emission signals of extrinsic oxygen deficient centres of the second type from singlet and directly excited triplet states, and we use them as a probe of structural inhomogeneity. Luminescence activity in sapphire (alpha-Al(2)O(3)) is studied as well and used as a model system to compare the optical properties of defects in silica with those of defects embedded in a crystalline matrix. Only for defects in silica did we observe a variation of the decay lifetimes with emission energy and a time dependence of the first moment…
Luminescence activity of surface and interior Ge-oxygen deficient centers in silica
2005
We report a comparative study on the optical activity of surface and interior Ge–oxygen deficient centers in pressed porous and sol–gel Ge-doped silica, respectively. The experimental approach is based on the temperature dependence of the two photoluminescence bands at 4.2 (singlet–singlet emission, S1! S0) and 3.1 eV (triplet–singlet emission, T1! S0), excited within the absorption band at about 5 eV. Our data show that the phonon assisted intersystem crossing process, linking the two excited electronic states, more effective for surface than for interior centers in the temperature range 5–300 K. For both centers, a distribution of the activation energies of the process is found. Based on th…
Computational evidence in favor of a two-state, two-mode model of the retinal chromophore photoisomerization
2000
In this paper we use ab initio multiconfigurational second-order perturbation theory to establish the intrinsic photoisomerization path model of retinal chromophores. This is accomplished by computing the ground state ( S 0 ) and the first two singlet excited-state ( S 1 , S 2 ) energies along the rigorously determined photoisomerization coordinate of the rhodopsin chromophore model 4- cis -γ-methylnona-2,4,6,8-tetraeniminium cation and the bacteriorhodopsin chromophore model all- trans -hepta-2,4,6-trieniminium cation in isolated conditions. The computed S 2 and S 1 energy profiles do not show any avoided crossing feature along the S 1 reaction path and maintain an energy gap >20 kcal⋅…
Through space singlet energy transfers in the light harvesting systems and cofacial bisporphyrin dyads
2010
Recent discoveries from our research groups on the photophysics of a few cofacial bisporphyrin dyads for through space singlet and triplet energy transfers raised several important investigations about the mechanism of energy transfers and energy migration in light-harvesting devices, notably LH II, in the heavily investigated purple photosynthetic bacteria. The key feature is that for face-to-face and slipped dyads with controlled structure using rigid spacers or spacers with limited flexibilities, our fastest rates for singlet energy transfer are in the 10 × 109 s -1 (i.e. 100 ps time scale) for donor-acceptor distances of ~3.5–3.6 Å. The time scale for energy transfers between different…
Comments on the through space singlet energy transfers and energy migration (exciton) in the light harvesting systems
2008
Recent findings on the photophysical investigations of several cofacial bisporphyrin dyads for through space singlet and triplet energy transfers raised several serious questions about the mechanism of the energy transfers and energy migration in the light harvesting devices, notably LH II, in the heavily studied purple photosynthetic bacteria. The key issue is that for simple cofacial or slipped dyads with controlled geometry using rigid spacers or spacers with limited flexibilities, the fastest possible rates for singlet energy transfer for three examples are in the 10 x 10(9)s(-1) (i.e. just in the 100 ps time scale) for donor-acceptor distances approaching 3.5-3.6 A. The reported time s…
Relaxation processes of point defects in vitreous silica from femtosecond to nanoseconds
2008
We studied ultrafast relaxation of localized excited states at Ge-related oxygen deficient centers in silica using femtosecond transient-absorption spectroscopy. The relaxation dynamics exhibits a biexponential decay, which we ascribe to the departure from the Frank-Condon region of the first excited singlet state in 240 fs, followed by cooling in ∼10 ps. At later times, a nonexponential relaxation spanning up to 40 ns occurs, which is fitted with an inhomogeneous distribution of nonradiative relaxation rates, following a chi-square distribution with one degree of freedom. This reveals several analogies with phenomena such as neutron reactions, quantum dot blinking, or intramolecular vibrat…
Optimal arrangements of 1,3-diphenylisobenzofuran molecule pairs for fast singlet fission.
2019
A simplified version of the frontier orbital model has been applied to pairs of C2, C2v, Cs, and C1 symmetry 1,3-diphenylisobenzofuran rotamers to determine their best packing for fast singlet fission (SF). For each rotamer the square of the electronic matrix element for SF was calculated at 2.2 × 109 pair geometries and a few thousand most significant physically accessible local maxima were identified in the six-dimensional space of mutual arrangements. At these pair geometries, SF energy balance was evaluated, relative SF rate constants were approximated using Marcus theory, and the SF rate constant kSF was maximized by further optimization of the geometry of the molecular pair. The proce…