De-excitation Mechanism Research Articles

Trajectory-dependent highly charged ion-induced electron yield from single-layer graphene

Abstract We study the neutralisation dynamics of highly charged ions by transmission through a free-standing single layer of graphene in dependence of the particle trajectory. Both the secondary electron yield and the neutralisation of the ion increase for increasing scattering angles (smaller impact parameters). This supports the current understanding of highly charged ion deexcitation, according to which the presence of an interatomic deexcitation mechanism with improved efficiency in the proximity of neighbours is necessary in addition to intraatomic radiative- and non-radiative decay pathways.

Revealing and Tuning the Photophysics of C=N Containing Photothermal Molecules: Excited State Dynamics Simulations.

Molecular photothermal conversion materials are recently attracting increasing attention for phototherapy applications. Herein we investigate the excitation and de-excitation processes of a photothermal molecule (C1TI) that is among the recently developed class of small-molecule-based photothermal imines with superb photothermal conversion efficiencies (PTCEs) up to 90% and a molecule (M2) that is constructed by replacing the amino group of C1TI with an H atom, via excited-state dynamics simulations based on the time-dependent density functional theory (TD-DFT). The simulations reveal fast (<150 fs of average time) nonradiative decays of the lowest excited singlet (S1) state to a conical intersection (CI) with the ground (S0) state in high yields (C1TI: 93.9% and M2: 87.1%). The fast decays, driven by C=N bond rotation to a perpendicular structural configuration, are found to be barrierless. The slight structural difference between C1TI and M2 leads to drastically different S0-S1 energy surfaces, especially M2 features a relatively much lower CI (0.8 eV in energy) and much more decay energy (1.0 eV) to approach the CI. This work provides insights into the de-excitation mechanisms and the performance tuning of C=N enabled photothermal materials.

Asymmetric Phenyl Substitution: An Effective Strategy to Enhance the Photosensitizing Potential of Curcuminoids.

Curcumin has been demonstrated to exhibit photosensitized bactericidal activity. However, the full exploitation of curcumin as a photo-pharmaceutical active principle is hindered by fast deactivation of the excited state through the transfer of the enol proton to the keto oxygen. Introducing an asymmetry in the molecular structure through acting on the phenyl substituents is expected to be a valuable strategy to impair this undesired de-excitation mechanism competing with the therapeutically relevant ones. In this study, two asymmetric curcumin analogs were synthesized and characterized as to their electronic-state transition spectroscopic properties. Fluorescence decay distributions were also reconstructed. Their analysis confirmed the substantial stabilization of the fluorescent state with respect to the parent compound. Nuclear magnetic resonance experiments were performed with the aim of determining the structural features of the keto–enol ring and the strength of the keto–enol hydrogen bond. Electronic structure calculations were also undertaken to elucidate the effects of substitution on the features of the keto–enol semi-aromatic system and the proneness to proton transfer. Finally, their singlet oxygen-generation efficiency was compared to that of curcumin through the 9,10-dimethylanthracene fluorescent assay.

Elucidating the effect of the spacer and the luminescence mechanism of SRB hosted in a LDH interlayer

The optical properties of LDH–DS/SRB powders were optimized by adjusting the alkyl chain length of the organic spacer between adjacent LDH sheets. In-depth study of the fluorescence dynamics enabled to propose a de-excitation mechanism.

Time evolution of CO2 ro-vibrational excitation in a nanosecond discharge measured with laser absorption spectroscopy

CO2 dissociation stimulated by vibrational excitation in non-equilibrium discharges has drawn lots of attention. Nanosecond (ns) discharges are known for their highly non-equilibrium conditions. It is therefore of interest to investigate the CO2 excitation in such discharges. In this paper, we demonstrate the ability for monitoring the time evolution of CO2 ro-vibrational excitation with a well-selected wavelength window around 2289.0 cm−1 and a single continuous-wave quantum cascade laser with both high accuracy and temporal resolution. The rotational and vibrational temperatures for both the symmetric and the asymmetric modes of CO2 in the afterglow of CO2 + He ns-discharge were measured with a temporal resolution of 1.5 μs. The non-thermal feature and the preferential excitation of the asymmetric stretch mode of CO2 were experimentally observed, with a peak temperature of Tv 3, max = 966 ± 1.5 K, Tv 1,2, max = 438.4 ± 1.2 K and T rot = 334.6 ± 0.6 K reached at 3 μs after the nanosecond pulse. In the following relaxation process, an exponential decay with a time constant of 69 μs was observed for the asymmetric stretch (001) state, consistent with the dominant deexcitation mechanism due to VT transfer with He and deexcitation on the wall. Furthermore, a synchronous oscillation of the gas temperature and the total pressure was also observed and can be explained by a two-line thermometry and an adiabatic process. The period of the oscillation and its dependence on the gas components is consistent with a standing acoustic wave excited by the ns-discharge.

Fission Fragment Intrinsic Spins and Their Correlations.

The intrinsic spins and their correlations are the least understood characteristics of fission fragments from both theoretical and experimental points of view. In many nuclear reactions, the emerging fragments are typically excited and acquire an intrinsic excitation energy and an intrinsic spin depending on the type of the reactions and interaction mechanism. Both the intrinsic excitation energies and the fragments' intrinsic spins and parities are controlled by the interaction mechanism and conservations laws, which lead to their correlations and determines the character of their deexcitation mechanism. We outline here a framework for the theoretical extraction of the intrinsic spin distributions of the fragments and their correlations within the fully microscopic real-time density-functional theory formalism and illustrate it on the example of induced fission of ^{236}U and ^{240}Pu, using two nuclear energy density functionals. These fission fragment intrinsic spin distributions display new qualitative features previously not discussed in literature. Within this fully microscopic framework, we extract for the first time the intrinsic spin distributions of fission fragments of ^{236}U and ^{240}Pu as well as the correlations of their intrinsic spins, which have been debated in literature for more than six decades with no definite conclusions so far.

Emission mechanism in single and co-doped Tb:Eu:CaZnOS

The study of new phosphors requires in-depth knowledge of the mechanisms and radiative emission paths and, with this aim, the study here reported focuses on the emission properties of CaZnOS crystals single doped with Terbium and co-doped with Terbium and Europium. By studying the optical properties and, in particular, the kinetics of recombination with time-resolved luminescence, the de-excitation mechanisms and the charge transfer processes have been established. A fundamental role is played by the defective centers and their efficient energy transfer process to the excited levels of Terbium, the mechanism being also active among co-doping rare earths (from Tb3+ to Eu3+), allowing further tuning of the emission properties. Beside photoluminescence, the study shows that in case of mechanical stimulus as well, the mechano-luminescence follows the same path, where the defective states of the matrix efficiently excite the levels of dopants, producing a green emission at 545 nm from Tb3+ and a red emission above 600 nm from Eu3+. Therefore, studying the relative ratio of dopants, it is shown how precisely tune across the visible part of the spectrum the mechano-luminescence emission.

Pressure-scaling characteristics of femtosecond two-photon laser-induced fluorescence of carbon monoxide.

Broadband femtosecond (fs) two-photon laser-induced fluorescence (TP-LIF) of the B1Σ+←X1Σ+, Hopfield-Birge system of carbon monoxide (CO) is believed to have two major advantages compared to narrowband nanosecond excitation. It should (i) minimize the effects of pressure-dependent absorption line broadening and shifting, and (ii) produce pressure-independent TP-LIF signals as the effect of increased quenching due to molecular collisions is offset by the increase in number density. However, there is an observed nonlinear drop in the CO TP-LIF signal with increasing pressure. In this work, we systematically investigate the relative impact of potential deexcitation mechanisms, including collisional quenching, forward lasing, attenuation of the source laser by the test cell windows or by the gas media, and a 2+1 photoionization process. As expected, line broadening and collisional quenching play minor roles in the pressure-scaling behavior, but the CO fs TP-LIF signals deviate from theory primarily because of two major reasons. First, attenuation of the excitation laser at high pressures significantly reduces the laser irradiance available at the probe volume. Second, a 2+1 photoionization process becomes significant as the number density increases with pressure and acts as a major deexcitation pathway. This work summarizes the phenomena and strategies that need to be considered for performing CO fs TP-LIF at high pressures.

Collision-mediated ultrafast decay of N2 fluorescence during fs-laser-induced filamentation.

We investigate experimentally spatiotemporal characteristics of fluorescence emission from fs-laser-induced filaments in air. Emissions accompanying the transitions of N2 (C3Πu-B3Πg) and N2+ (B2Σu+-X2Σg+) are dominant. The decay dynamics of fluorescence from different radial positions and longitudinal sections of a filament column are obtained along with high resolution spectra. A decay curve contains two exponential components: a fast one (with a decay time constant ∼10s ps), and a slow one (∼sub-ns). The lifetime of the N2 fluorescence is about three orders shorter than its spontaneous emission lifetime, indicating that most of the N2 molecules in the excited state (C3Πu) are de-excited through collision. Different de-excitation mechanisms of N2 (C3Πu) molecules contributing to fluorescence decay constants, e.g., the e--N2, N2-N2, and O2-N2 collisions, are elucidated. We analyze the variations of decay constants together with corresponding fluorescence intensities, and obtain temperature distributions by fitting band spectra of N2 molecules and N2+ ions with a synthetic spectral model. Our results suggest that the fast and slow decay processes originate from the e--N2 and O2-N2 collisions, respectively.

Polyaniline photoluminescence quenching induced by single-walled carbon nanotubes enriched in metallic and semiconducting tubes

The influence of single-walled carbon nanotubes enriched in semiconductor (S-SWNTs) and metallic (M-SWNTs) tubes on the photoluminescence (PL) of polyaniline (PANI), electrosynthesized in the presence of the H2SO4 and HCl solutions, is reported. The emission bands peaked at 407–418 and 440–520 nm indicate that the electropolymerization of aniline (ANI) leads to the formation of short and longer macromolecular chains (MCs), respectively. We demonstrate that the reaction product consists of ANI tetramers (TT) and trimers (TR) as well as PANI-salt. Using Raman scattering and IR absorption spectroscopy, a covalent functionalization of SWNTs with shorter and longer MCs of PANI-salt is demonstrated. The presence of S-SWNTs and M-SWNTs induces a decrease in ANI TT weight in the reaction product mass consisting in S-SWNTs and M-SWNTs covalently functionalized with PANI-emeraldine salt (ES) and PANI-leucoemeraldine salt (LS), respectively. A PANI PL quenching is reported to be induced of the S-SWNTs and M-SWNTs. A de-excitation mechanism is proposed to explain PANI PL quenching.

Coherent gamma photon generation in a Bose–Einstein condensate of [formula omitted]Cs

We have identified a mechanism of collective nuclear de-excitation in a Bose–Einstein condensate of 135Cs atoms in their isomeric state, 135mCs, suitable for the generation of coherent gamma photons. The process described here relies on coherence transfer from the Bose–Einstein condensate to the photon field, leading to collective decay triggered by spontaneous emission of a gamma photon. The mechanism differs from single-pass amplification, which cannot occur in atomic systems due to the nuclear recoil and the associated large shift between absorption and emission lines, nor does it require the large densities necessary for standard Dicke super-radiance. This overcomes the limitations that have been hindering the production of coherent gamma photons in many systems. Therefore, we propose an approach for generation of coherent gamma rays, which relies on a combination of well established techniques of nuclear and atomic physics, and can be realized with currently available technology.

Modulation of the Photophysical Properties of β-substituted BODIPY Dyes.

Photophysical properties of BODIPY dyes containing acetyl acetone and benzoyl acetone BF2 unit as an electron accepting substituent at beta position linked via double bond have been investigated using a wide range of solvents of different polarities. The substitution effect at beta position of the BODIPY dyes on their absorption, emission and quantum yield of fluorescence have been the aim of present study. For the synthesized BODIPY dyes fluorescence quantum yields and lifetimes show very sharp decrease with an increase in the solvent polarity, suggesting the involvement of highly polar ICT state de-excitation mechanism along with the local excitation process. The polarity dependent changes in average fluorescence life time and quantum yield values rationalize the formation of ICT states.

Interatomic Coulombic Decay: The Mechanism for Rapid Deexcitation of Hollow Atoms.

The impact of a highly charged ion onto a solid gives rise to charge exchange between the ion and target atoms, so that a slow ion gets neutralized in the vicinity of the surface. Using highly charged Ar and Xe ions and the surface-only material graphene as a target, we show that the neutralization and deexcitation of the ions proceeds on a sub-10fs time scale. We further demonstrate that a multiple Interatomic Coulombic Decay (ICD) model can describe the observed ultrafast deexcitation. Other deexcitation mechanisms involving nonradiative decay and quasimolecular orbital formation during the impact are not important, as follows from the comparison of our experimental data with the results of first-principles calculations. Our method also enables the estimation of ICD rates directly.

Mo6 cluster-based compounds for energy conversion applications: comparative study of photoluminescence and cathodoluminescence

We report the photoluminescence (PL) and cathodoluminescence (CL) properties of face-capped [Mo6Xi8La6]2− (X = Cl, Br, I; L = organic or inorganic ligands) cluster units. We show that the emission of Mo6 metal atom clusters depends not only on the nature of X and L ligands bound to the cluster and counter-cations, but also on the excitation source. Seven members of the AxMo6Xi8La6 series (A = Cs+, (n-C4H9)4N+, NH4+) were selected to evaluate the influence of counter-cations and ligands on de-excitation mechanisms responsible for multicomponent emission of cluster units. This study evaluates the ageing of each member of the series, which is crucial for further energy conversion applications (photovoltaic, lighting, water splitting, etc.).

Ultrafast photo-induced charge transfer of 1-naphthol and 2-naphthol to halocarbon solvents

We explore the fluorescence quenching of 1-naphthol and 2-naphthol in halocarbon solvents by using time-correlated single-photon-counting, femtosecond IR-spectroscopy and quantum chemistry computations. We find that halocarbon solvents facilitate a de-excitation mechanism via solute-solvent electron transfer. Decay rates are modulated by close contact interactions between the π-electronic structure of naphthols and halocarbon molecules in their first solvation shell. 1-naphthol exhibits faster decay rates than 2-naphthol due to closer interactions with the solvent.

High precision measurements on fission-fragment de-excitation

In recent years nuclear fission has gained renewed interest both from the nuclear energy community and in basic science. The first, represented by the OECD Nuclear Energy Agency, expressed the need for more accurate fission cross-section and fragment yield data for safety assessments of Generation IV reactor systems. In basic science modelling made much progress in describing the de-excitation mechanism of neutron-rich isotopes, e.g. produced in nuclear fission. Benchmarking the different models require a precise experimental data on prompt fission neutron and γ-ray emission, e.g. multiplicity, average energy per particle and total dissipated energy per fission, preferably as function of fission-fragment mass and total kinetic energy. A collaboration of scientists from JRC Geel (formerly known as JRC IRMM) and other institutes took the lead in establishing a dedicated measurement programme on prompt fission neutron and γ-ray characteristics, which has triggered even more measurement activities around the world. This contribution presents new advanced instrumentation and methodology we use to generate high-precision spectral data and will give a flavour of future data needs and opportunities.

Vibronic transitions in the alkali-metal (Li, Na, K, Rb) – alkaline-earth-metal (Ca, Sr) series: A systematic analysis of de-excitation mechanisms based on the graphical mapping of Frank-Condon integrals

Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)-- alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.

Prompt fissionγ-ray data from spontaneous fission and the mechanism of fission-fragment de-excitation

The investigation of prompt γ-ray emission in nuclear fission has a great relevance for the assessment of prompt heat generation in a reactor core and for the better understanding of the de-excitation mechanism of fission fragments. Some years ago experimental data was scarce and available only from a few fission reactions, 233,235 U(nth , f), 239 Pu(nth , f), and 252 Cf(sf). Initiated by a high priority data request published by the OECD/NEA a dedicated prompt fission γ-ray measurement program is being conducted at the Joint Research Centre Geel. In recent years we obtained new and accurate prompt fission γ-ray spectrum (PFGS) characteristics (average number of photons per fission, average total energy per fission and mean photon energy) from 252 Cf(sf), 235 U(nth , f) and 239,241 Pu(nth , f) within 2% of uncertainty. In order to understand the dependence of prompt fission γ-ray emission on the compound nuclear mass and excitation energy, we started a first measurement campaign on spontaneously fissioning plutonium and curium isotopes. Results on PFGS characteristics from 240,242 Pu(sf) show a dependence on the fragment mass distribution rather than on the average prompt neutron multiplicity, pointing to a more complex competition between prompt fission γ-ray and neutron emission.

BOIMPY: Fluorescent Boron Complexes with Tunable and Environment‐Responsive Light‐Emitting Properties

A series of air-stable boron complexes 1-5 were prepared by using N-aryl iminopyrrolide ligands. Designed as minimalist structural mimics of the privileged BODIPY motif, these new BOIMPY (BOron complexes of IMinoPYrrolide ligands) fluorophores feature low molecular symmetry that promotes emission from CT-type excited states with large Stokes shifts and little self-quenching. Through comparative studies on the homologous set of compounds 1-4, we have confirmed that a delicate interplay between conformational twisting and donor-acceptor interaction dictates the mechanism of de-excitation, which responds sensitively to solvent polarity as well as protonation states. Over a wide visible spectral range, the structure-dependent light-emitting properties of BOIMPY molecules are well manifested, even in the solid-state. In order to exploit the environment-sensitive nature of CT-type emission, the BOIMPY motif was elaborated further into a bioprobe molecule 5. Live-cell fluorescence imaging studies have established that 5 is localized exclusively at lipid droplets to produce well-resolved staining patterns without affecting cell viability. These findings promise future elaboration of BOIMPY-based functional molecules for applications in biological imaging, chemical sensing, and molecular switching.

On the Photoluminescence Linearity of Eu2+ Based LED Phosphors upon High Excitation Density

This work deals with the saturation behavior of Eu2+ doped luminescent materials. Eu2+ activated phosphors, excited by high radiance pump sources, like high power LEDs or Laser Diodes, offer considerable potential for high radiance conversion in Solid State Lighting. Remarkably, theoretical arguments suggest that the radiance of the luminescent spot should increase linearly with the excitation density of the incoming light source up to 1 kW/mm2. In practice, however, thermal quenching and (non-thermal) optical saturation limit the maximum attainable radiance of the luminescent material. We present experimental data of the widely applied red emitting LED phosphors (Ca,Ba)2SiO4:Eu2+ (OSE), Ba2Si5N8:Eu2+ (258:Eu), and CaAlSiN3:Eu2+ (CASN:Eu) in which these limits have been investigated. High excitation fluxes are achieved using laser pumping at 405 nm up to 800 W/mm2. In case of 258:Eu and CASN:Eu, optical pumping intensities have been shown to produce a significant efficiency depreciation already at low pump powers, which does not correlate with the relatively short Eu2+ luminescence lifetime (~ 1 μs). We assume a de-excitation mechanism that depletes the excited state [Xe]4f 65d 1 to the conduction band of the host structure, which bottlenecks the limit maximum pump intensities. We find that the investigated Eu2+ phosphors tend to show different efficiency depreciation. Finally, we use a rate equation model to simulate this nonlinear optical pumping. Figure 1