Search results for "EXCITATION"

Radiative Cooling of a Small Metal Cluster: The Case ofV13+

1999

Size-selected stored metal cluster ions, ${\mathrm{V}}_{13}^{+}$, have been heated by photoexcitation ( $\ensuremath{\lambda}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}730$ to 229 nm) to well-defined excitation energies corresponding to temperatures between 1000 and 2100 K. A millisecond pump-probe photodissociation technique was applied to measure the time-resolved radiative cooling. The observed decay rates are directly related to the radiative energy loss and are explained quantitatively by the competing processes of photoemission and atom evaporation.

Theory of Nuclear Quantum Dynamics Simulations

2016

In Chap. 2, we have seen that the theoretical study of a molecular system is, in a vast majority of cases, separated in two steps. In a first step, the electronic structure of the system is studied by solving the electronic Schrodinger equation with fixed nuclei. This approach, combined with geometry optimization techniques, allows one to locate the important features of the various potential energy surfaces (PESs) of the electronic states of interest. In the context of photochemistry, as seen in Chap. 3, this approach allows one to characterize the various decay pathways of the molecule after photoexcitation. This information can then be used to interpret the various decay time constants o…

Charge-Separation and Charge-Recombination Rate Constants in a Donor–Acceptor Buckybowl-Based Supramolecular Complex: Multistate and Solvent Effects

2021

The kinetics of the nonradiative photoinduced processes (charge-separation and charge-recombination) experimented in solution by a supramolecular complex formed by an electron-donating bowl-shaped truxene-tetrathiafulvalene (truxTTF) derivative and an electron-accepting fullerene fragment (hemifullerene, C30H12) has been theoretically investigated. The truxTTF·C30H12 heterodimer shows a complex decay mechanism after photoexcitation with the participation of several low-lying excited states of different nature (local and charge-transfer excitations) all close in energy. In this scenario, the absolute rate constants for all of the plausible charge-separation (CS) and charge-recombination (CR)…

Nonadiabatic orientation, toroidal current, and induced magnetic field in BeO molecules.

2008

It is predicted that oriented BeO molecules would give rise to unprecedentedly strong, unidirectional electric ring current and an associated magnetic field upon excitation by a right or left circularly polarized laser pulse into the first excited degenerate singlet state. The strong toroidal electric ring current of this state is dominated by the ring current of the 1π± orbital about the molecular axis. Our predictions are based on the analysis of the orbital composition of the states involved and are substantiated by high level electronic structure calculations and wavepacket simulations of the laser-driven orientation and excitation dynamics. Luis.Serrano@uv.es

2014

There have been a number of recent experimental investigations of the nonadiabatic relaxation dynamics of aniline following excitation to the first three singlet excited states, 1(1)ππ*, 1(1)π3s/πσ* and 2(1)ππ*. Motivated by differences between the interpretations of experimental observations, we have employed CASSCF and XMCQDPT2 calculations to explore the potential energy landscape and relaxation pathways of photoexcited aniline. We find a new prefulvene-like MECI connecting the 1(1)ππ* state with the GS in which the carbon-atom carrying the amino group is distorted out-of-plane. This suggests that excitation above the 1(1)π3s/πσ* vertical excitation energy could be followed by electronic…

Dual Luminescence, Interligand Decay, and Nonradiative Electronic Relaxation of Cyclometalated Iridium Complexes in Solution

2016

Femtosecond broadband photoluminescence studies are presented for Ir(ppy)3 (Ir1), Ir(ppy)2(pic) (Ir2), Ir(ppy)2(bpy)(PF6) (Ir3), Ir(ppz)3 (Ir4), and Ir(ppz)2dipy (Ir5) (where ppy = 2-phenylpyridine, pic = picolinate, bpy = 2,2′-bipyridine, ppz = 1-phenylpyrazole, and dipy = 5-phenyldipyrrinato) in solution. Upon 400-nm excitation of Ir1–Ir3, we observed a prompt population of the lowest MLCT states. The higher states decay on an ultrafast time scale (3MLCT state undergoes further vibrational relaxation on a 1-ps time scale. In Ir3, this relaxation is accompanied by an interligand decay from the ppy to the bpy ligand in ∼1.5 ps. For the ppy-containing complexes (Ir1 and Ir2), we found that, …

Photoluminescence activity in natural silica excited in the vacuum-UV range

1999

Abstract We report an experimental study on the optical absorption and photoluminescence detected in samples of natural silica. Our results show that the two emission bands, β (∼3.1 eV) and α E (∼4.3 eV), have an excitation profile in the vacuum ultraviolet region with a maximum at ∼7.5 eV. This excitation profile indicates that, in terms of energy levels of the luminescent defect, there is a transition from a ground state, S 0 , to a second excited state, S 2 , able to excite PL emission, in addition to the well known transition corresponding to the optical absorption band, B 2β . Our data are in a quantitative agreement with `ab initio' calculations carried out for a two-fold coordinated …

Cathodoluminescence mechanism of crystalline Gd2SiO5:Ce

1993

Complex luminescence decay kinetics have been observed in Gd2SiO5:Ce crystals under electron beam irradiation. Absorption and photoluminescence excitation spectra, decay kinetics in various excitation bands over a wide range of photon energies from 3.6 to 7.0 eV in the temperature region from 80 to 400 K as well as the spectra of the glow curve creation efficiency at 80 K are examined. It is shown that the free electronic excitations produced, depending on the absorbed photon energy, have different recombination mechanisms finally leading to the radiative transitions between the 5d2E configuration and the 4f configuration of the Ce3+ ion. At hvexc < 6.1 eV a single exponential decay caused …

Ultrafast Relaxation Dynamics of Osmium−Polypyridine Complexes in Solution

2013

We present steady-state absorption and emission spectroscopy and femtosecond broadband photoluminescence up-conversion spectroscopy studies of the electronic relaxation of Os(dmbp)(3) (Os1) and Os(bpy)(2)(dpp) (Os2) in ethanol, where dmbp is 4,4'-dimethyl-2,2'-biypridine, bpy is 2,2'-biypridine, and dpp is 2,3-dipyridyl pyrazine. In both cases, the steady-state phosphorescence is due to the lowest (MLCT)-M-3 state, whose quantum yield we estimate to be <= 5.0 x 10(-3). For Os1, the steady-state phosphorescence lifetime is 25 ns. In both complexes, the photoluminescence excitation spectra map the absorption spectrum, pointing to an excitation wavelength-independent quantum yield. The ultrafa…

Luminescence properties of nonbridging oxygen hole centers at the silica surface

2009

Abstract Two variants of the surface-nonbridging oxygen hole center, ( Si–O)3Si–O• and ( Si–O)2(H–O)Si–O•, stabilized in porous films of silica nano-particles were investigated by time resolved luminescence excited in the visible and UV spectral range by a tunable laser system. Both defects emit a photoluminescence around 2.0 eV with an excitation spectrum evidencing two maxima at 2.0 and 4.8 eV, this emission decreases by a factor ∼2 on increasing the temperature from 8 up to 290 K. However, the different local structure influences the emission lineshape, the quantum yield and the decay lifetime. Such peculiarities are discussed on the basis of the symmetry properties of these defects.