Depopulation Of Excited State Research Articles

Effect of neodymium ions on the photosensitivity of photo-thermo-refractive glass

Neodymium doping of photo-thermo-refractive (PTR) glass leads to a fast non-radiative depopulation of excited states of cerium ions, which are responsible for the glass photosensitivity. The non-radiative energy transfer from cerium to neodymium ions results in a decrease in the efficiency of photoelectron generation under UV irradiation. Emission spectra and fluorescence decay curves of cerium ions under UV excitation were investigated. Absorption spectra of the glasses were obtained as well to distinguish the reabsorption processes and the non-radiative energy transfer mechanisms. It was found that as Nd2O3 concentration increases from 0 to 2 mol%, cerium ions average lifetime decreases from 44.5 to 28 ns, while the energy transfer efficiency reaches 37 %. It was also found that Förster resonance energy transfer may compete with other relaxation mechanisms and the Förster distance for the Ce3+-Nd3+ pair in PTR glass is ∼0.33 nm. This study has important implications for future research; it informs future studies on optimizing the photosensitivity of the PTR glass and choosing rare-earth activators.

Spectral Relaxation Imaging Microscopy II: Complex Dynamics.

The dynamics of condensed matter can be measured by the time-dependent Stokes shift of a suitable fluorescent probe. The time-dependent spectral correlation function is typically described by one or more spectral relaxation correlation times, which, in liquid solvents, characterize the timescales of the dipolar relaxation processes around the excited-state probe. The phasor plot provides a powerful approach to represent and analyze time and frequency-domain data acquired as images, thus providing a spatial map of spectral dynamics in a complex structure such as a living cell. Measurements of the phase and modulation at two emission wavelength channels were shown to be sufficient to extract a single excited-state lifetime and a single spectral relaxation correlation time, supplying estimates of the mean rate of excited-state depopulation and the mean rate of spectral shift. In the present contribution, two more issues were addressed. First, the provision of analytic formulae allowing extraction of the initial generalized polarization and the relaxed generalized polarization, which characterize the fluorescence spectrum of the unrelaxed state and the fully relaxed state. Second, improved methods of model discrimination and model parameter extraction for more complex spectral relaxation phenomena. The analysis workflow was illustrated with examples from the literature.

New method for level-lifetime measurements with thick scintillators

Level lifetimes provide key insight into the structure of atomic nuclei and serve as stringent tests of theoretical descriptions. Though several methods for determining level lifetimes exist for both reaction measurements and decay studies, here the focus is on techniques involving the direct measurement of time differences between population and subsequent depopulation of excited states. The techniques presented herein are broadly applicable across multiple timing ranges, but the approach is specifically described for the βγ timing method. A multi-step, amplitude-dependent time walk correction and timing resolution corrections were employed to address the data analysis complications that arise from using thick scintillators for electron detection. Subsequently, a new Monte Carlo method utilizing measured detector responses obtained from the data, coupled with chi-square minimization, is presented for extracting excited state lifetimes ≳ 100 picoseconds. The framework of this Monte Carlo method is developed for the decay of a state in 68Zn with a known 1.6 ps half life, which is considered prompt given the detection sensitivity of the technique, and then benchmarked using two other excited states in neutron-rich Ni isotopes with 120(34) ps and 1.05(3) ns half lives. Using this new method which takes into account the thick scintillator used, these same half lives were measured to be 135(10) ps and 1.04(24) ns, respectively. The overall good agreement demonstrates the validity of the technique.

Ultrafast excited states dynamics of metal ion complexes of the carotenoid astaxanthin

Carotenoids are natural compounds with multiple functions in biological systems. They exhibit rich photophysics that can be modified by changes in properties of their local environments. Here we present time-resolved spectroscopy data from complexes resulting from interaction of the carotenoid astaxanthin with Zn2+ and Cu2+ ions. The astaxanthin-metal complexes exhibit significant alteration of their excited-state dynamics, resulting in enhancement of the charge transfer character of the lowest excited state, S1/ICT. The S1/ICT lifetime of pure astaxanthin, 4.4 ps, is shortened to 3.9 ps and 2.6 ps for astaxanthin-Zn and astaxanthin-Cu complex, respectively. The lifetime shortening is attributed to prolongation of effective conjugation caused by interaction of metal ions with keto oxygen at the terminal rings of astaxanthin. The significant shortening of the S1/ICT lifetime of astaxanthin-Cu complex also results in observation of the S* signal, which is likely due to a hot ground state generated by rapid depopulation of excited states.

Orbital anisotropy of heavy fermion Ce2IrIn8 under crystalline electric field and its energy scale

We investigate the temperature $(T)$ evolution of orbital anisotropy and its effect on spectral function and optical conductivity in ${\mathrm{Ce}}_{2}{\mathrm{IrIn}}_{8}$ using a first-principles dynamical mean-field theory combined with density functional theory. The orbital anisotropy develops by lowering $T$ and it is intensified below a temperature corresponding to the crystalline-electric field (CEF) splitting size. Interestingly, the depopulation of CEF excited states leaves a spectroscopic signature, ``shoulder,'' in the $T$-dependent spectral function at the Fermi level. From the two-orbital Anderson impurity model, we demonstrate that CEF splitting size is the key ingredient influencing the emergence and the position of the ``shoulder.'' Besides the two conventional temperature scales ${T}_{K}$ and ${T}^{*}$, we introduce an additional temperature scale to deal with the orbital anisotropy in heavy fermion systems.

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Fluorinated Porphycenes: Synthesis, Spectroscopy, Photophysics, and Tautomerism.

Six porphycenes have been synthesized, bearing one, two, or three fluorine atoms attached directly to the 18-π-electron system at the meso positions. These novel compounds have been characterized by structural, electrochemical, and spectral techniques, combined with quantum chemical calculations. In three fluoroporphycenes, the unsymmetric substitution pattern leads to the presence of two nonequivalent trans tautomeric forms. They have been identified using electronic absorption, emission, and magnetic circular dichroism spectroscopies. Their relative energies have been estimated for the ground and lowest excited electronic states. Tautomerization potential is quasi-symmetric in S0 , but becomes strongly nonsymmetric in S1 . Femtosecond transient absorption studies allowed determination of tautomerization rates, larger and similar for both directions of the double hydrogen transfer in S0 , lower and disparate in S1 . Fluoroporphycenes emerge as good candidates for detailed studies of mechanisms of double hydrogen transfer, as well as processes responsible for rapid radiationless excited state depopulation.

Defect State Assisted Z-scheme Charge Recombination in Bi2O2CO3/Graphene Quantum Dot Composites For Photocatalytic Oxidation of NO

In this work, we explored the photoinduced charge carriers dynamics rationalizing the photocatalytic oxidation of NO over N-doped Bi2O2CO3/graphene quantum dots composites(N-BOC/GQDs) via time-resolved photoluminescence (TRPL). Under visible light illumination, only GQDs can be photoexcited and inject electrons to N-BOC within 0.5 ns. Under UV light irradiation, the interfacial Z-scheme heterojunction recombination between the electrons in N-BOC and holes in GQDs dominate the depopulation of excited states within 0.36 ns. Such efficient Z-scheme recombination regardless of the large energy difference (1.66 eV) is mediated by the interfacial oxygen vacany defect states characterized by both density functional theory calculations (DFT) and electron paramagnetic resonance (EPR) measurement. This finding provide a novel strategic view to improve the photocatalytic performance of the nanocomposite by interfacial engineering

Ultrafast spectroscopy of biliverdin dimethyl ester in solution: pathways of excited-state depopulation.

Biliverdin is a bile pigment that has a very low fluorescence quantum yield in solution, but serves as a chromophore in far-red fluorescent proteins being developed for bio-imaging. In this work, excited-state dynamics of biliverdin dimethyl ether (BVE) in solvents were investigated using femtosecond (fs) and picosecond (ps) time-resolved absorption and fluorescence spectroscopy. This study is the first fs timescale investigation of BVE in solvents, and therefore revealed numerous dynamics that were not resolved in previous, 200 ps time resolution measurements. Viscosity- and isotope-dependent experiments were performed to identify the contributions of isomerization and proton transfer to the excited-state dynamics. In aprotic solvents, a ∼2 ps non-radiative decay accounts for 95% of the excited-state population loss. In addition, a minor ∼30 ps emissive decay pathway is likely associated with an incomplete isomerization process around the C15[double bond, length as m-dash]C16 double bond that results in a flip of the D-ring. In protic solvents, the dynamics are more complex due to hydrogen bond interactions between solute and solvent. In this case, the ∼2 ps decay pathway is a minor channel (15%), whereas ∼70% of the excited-state population decays through an 800 fs emissive pathway. The ∼30 ps timescale associated with isomerization is also observed in protic solvents. The most significant difference in protic solvents is the presence of a >300 ps timescale in which BVE can decay through an emissive state, in parallel with excited-state proton transfer to the solvent. Interestingly, a small fraction of a luminous species, which we designate lumin-BVE (LBVE), is present in protic solvents.

Resolving environmental microheterogeneity and dielectric relaxation in fluorescence kinetics of protein

The fluorescence intensity decay of protein is easily measurable and reports on the intrinsic fluorophore-local environment interactions on the sub-nm spatial and sub-ns temporal scales, which are consistent with protein activity in numerous biomedical and industrial processes. This makes time-resolved fluorescence a perfect tool for understanding, monitoring and controlling these processes at the molecular level, but the complexity of the decay, which has been traditionally fitted to multi-exponential functions, has hampered the development of this technique over the last few decades. Using the example of tryptophan in HSA we present the alternative to the conventional approach to modelling intrinsic florescence intensity decay in protein where the key factors determining fluorescence decay, i.e. the excited-state depopulation and the dielectric relaxation (Toptygin and Brand 2000 Chem. Phys. Lett. 322 496–502), are represented by the individual relaxation functions. This allows quantification of both effects separately by determining their parameters from the global analysis of a series of fluorescence intensity decays measured at different detection wavelengths. Moreover, certain pairs of the recovered parameters of tryptophan were found to be correlated, indicating the influence of the dielectric relaxation on the transient rate of the electronic transitions. In this context the potential for the dual excited state depopulation /dielectric relaxation fluorescence lifetime sensing is discussed.

Reversible oxygen addition on a triplet sensitizer molecule: protection from excited state depopulation.

We demonstrate that photoactivated oxygen addition to diphenylanthracene moities can be used as a tool for protection of porphyrin's phosphorescence against oxygen quenching. Phosphorescent palladium(II) tetrabenzoporphyrin, covalently linked to four diphenylanthracene moieties, was synthesized and studied. Upon irradiation with ambient light or red laser in solution in air, addition of oxygen and formation of the corresponding endoperoxides were observed. Heating of the irradiated samples afforded the parent porphyrin material.

Application of Ultrashort DUV Pulse Laser to Study the Primary Dynamic Process of Molecules in Vitamin D Biosynthesis

The dynamics of electronic dynamics of precursor of vitamin D3, 7-dehydrocholesterol (7-DHC), is investigated by deep ultraviolet (DUV) transient absorption spectroscopy using 11 fs pulses. The electronic transition energy is modulated by vibrational modes having frequencies of 1183, 1347, 1459, 1603, and 1766 cm‒1. The most pronounced frequency feature is a shift of the central frequency from 1615 to 1603 cm‒1, which is discussed in terms of excited state depopulation of 7-DHC. We report the absorption spectra of 1B2 excited state of 7-DHC and cZc-previtamin D3 (czc-Pre) generated through the ring opening in 7-DHC calculated on the basis of kinetic analysis of transient absorbance changes.

Substituent and solvent effects on the excited state deactivation channels in anils and boranils.

Differently substituted anils (Schiff bases) and their boranil counterparts lacking the proton-transfer functionality have been studied using stationary and femtosecond time-resolved absorption, fluorescence, and IR techniques, combined with quantum mechanical modelling. Dual fluorescence observed in anils was attributed to excited state intramolecular proton transfer. The rate of this process varies upon changing solvent polarity. In the nitro-substituted anil, proton translocation is accompanied by intramolecular electron transfer coupled with twisting of the nitrophenyl group. The same type of structure is responsible for the emission of the corresponding boranil. A general model was proposed to explain different photophysical responses to different substitution patterns in anils and boranils. It is based on the analysis of changes in the lengths of CN and CC bonds linking the phenyl moieties. The model allows predicting the contributions of different channels that involve torsional dynamics to excited state depopulation.

Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations.

Progress in our understanding of ultrafast light-induced processes in molecules is best achieved through a close combination of experimental and theoretical approaches. Direct comparison is obtained if theory is able to directly reproduce experimental observables. Here, we present a joint approach comparing time-resolved photoelectron spectroscopy (TRPES) with ab initio multiple spawning (AIMS) simulations on the MS-MR-CASPT2 level of theory. We disentangle the relationship between two phenomena that dominate the immediate molecular response upon light absorption: a spectrally dependent delay of the photoelectron signal and an induction time prior to excited state depopulation in dynamics simulations. As a benchmark molecule, we have chosen hexamethylcyclopentadiene, which shows an unprecedentedly large spectral delay of (310 ± 20) fs in TRPES experiments. For the dynamics simulations, methyl groups were replaced by "hydrogen atoms" having mass 15 and TRPES spectra were calculated. These showed an induction time of (108 ± 10) fs which could directly be assigned to progress along a torsional mode leading to the intersection seam with the molecular ground state. In a stepladder-type approach, the close connection between the two phenomena could be elucidated, allowing for a comparison with other polyenes and supporting the general validity of this finding for their excited state dynamics. Thus, the combination of TRPES and AIMS proves to be a powerful tool for a thorough understanding of ultrafast excited state dynamics in polyenes.

Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing the photodissociation and depopulating the excited S(2) or S(3) state molecules to the lowest T(1) state with a rate of ∼2.5 ps after a delayed onset of ∼3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T(1) excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T(1) excited state. The measured ultrafast formation of T(1) excited state supports the existence of the surface intersections of S(2)/S(1), S(2)/T(2), and S(1)/T(1)/T(2), and the large T(1) quantum yield of ∼0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.

Ultrafast Excited-state Deactivation of Flavins Bound to Dodecin

Dodecins, a group of flavin-binding proteins with a dodecameric quaternary structure, are able to incorporate two flavins within each of their six identical binding pockets building an aromatic tetrade with two tryptophan residues. Dodecin from the archaeal Halobacterium salinarum is a riboflavin storage device. We demonstrate that unwanted side reactions induced by reactive riboflavin species and degradation of riboflavin are avoided by ultrafast depopulation of the reactive excited state of riboflavin. Intriguingly, in this process, the staggered riboflavin dimers do not interact in ground and photoexcited states. Rather, within the tetrade assembly, each riboflavin is kept under the control of the respective adjacent tryptophan, which suggests that the stacked arrangement is a matter of optimizing the flavin load. We further identify an electron transfer in combination with a proton transfer as a central element of the effective excited state depopulation mechanism. Structural and functional comparisons of the archaeal dodecin with bacterial homologs reveal diverging evolution. Bacterial dodecins bind the flavin FMN instead of riboflavin and exhibit a clearly different binding pocket design with inverse incorporations of flavin dimers. The different adoption of flavin changes photochemical properties, making bacterial dodecin a comparably less efficient quencher of flavins. This supports a functional role different for bacterial and archaeal dodecins.

Scintillator-oriented combinatorial search in Ce-doped (Y,Gd)3(Ga,Al)5O12 multicomponent garnet compounds

Ce-doped (YyGd1−y)3(GaxAl1−x)5O12(x = 0, 1, 2, 3, 4 and y = 1, 2, 3) single crystals are grown by the micro-pulling down method. X-ray diffraction and electron probe microanalysis techniques are employed to check their structure and chemical composition, respectively. Optical and photoluminescence characteristics are measured and radioluminescence spectra, light yield and scintillation decay measurements are further made to evaluate the scintillation performance. We show that balanced Gd and Ga admixture in the Y3Al5O12 structure can considerably increase the scintillation efficiency, and the spectrally corrected light yield value exceeds 44 000 photon MeV−1. Scintillation decay times approach that of Ce3+ photoluminescence decay and an additional less intense slower component is also observed. Physical aspects of energy transfer process and 5d1 excited state depopulation are discussed. The micro-pulling down technique is shown as an ideal tool for a directed combinatorial search for targeted single crystal compositions to reveal those with the highest figure-of-merit for a given application field.

Depletion of the excited state population in negative ions using laser photodetachment in a gas-filled RF quadrupole ion guide

The depopulation of excited states in beams of negatively charged carbon and silicon ions was demonstrated using collisional detachment and laser photodetachment in a radio-frequency quadrupole ion guide filled with helium. The high-lying, loosely bound 2D excited state in C− was completely depleted through collisional detachment alone, which was quantitatively determined within 6%. For Si− the combined signal from the population in the 2P and 2D excited states was only partly depleted through collisions in the cooler. The loosely bound 2P state was likely to be completely depopulated, and the more tightly bound 2D state was partly depopulated through collisions. 98(2)% of the remaining 2D population was removed by photodetachment in the cooler using less than 2 W laser power. The total reduction of the excited population in Si−, including collisional detachment and photodetachment, was estimated to be 99(1)%. Employing this novel technique to produce a pure ground state negative ion beam offers possibilities of enhancing selectivity, as well as accuracy, in high-precision experiments on atomic as well as molecular negative ions.

Optical characterizations of Er3+-doped KLa(PO3)4 phosphate crystals

Abstract Absorption spectra were recorded for the three samples of KLa 1− x Er x (PO 3 ) 4 crystal, where x = 0.025, 0.05 and 1, at room temperature in the 400–900 nm spectral range. Fluorescent emissions from the 4 S 3/2 and 4 F 9/2 multiplets were observed under pulsed laser excitation in the 2 H 11/2 multiplet ( λ exc = 532 nm ) and in the 4 G 9/2 multiplet (355 nm). The time-resolved luminescence of these emissions has also been studied. The decays are shown to be exponential, with decay times on the order of 1 μs, independently of the erbium content. No significant lengthening of the decay time is observed as erbium concentration decreases from 100 to 2.5 at.%. Non-radiative relaxations related to multiphonon emission have been evoked to be at the origin of the excited state depopulation in the Er 3+ -doped KLa(PO 3 ) 4 crystals studied. The emission spectra of the lasing transition 4 I 13/2 → 4 I 15/2 in Er 3+ -doped KLa(PO 3 ) 4 phosphate crystals have also been analyzed. The influence of the erbium concentration on this electronic transition has been discussed as well. It was observed that the increase of Er 3+ ion concentration, in the 2.5–100 at.% range, results in a spectral broadening of the 1.54 μm emission band. Reabsorption has been evoked as the main mechanism to explain the broadening of the 4 I 13/2 → 4 I 15/2 emission line.

Role of Mode-mode Coupling in Short-time Excited State Decay

Master equation of a relevant electronic and vibrational system is derived for a special diabatic basis corresponding to vertical processes. It is shown that bath modes contribute dynamically to the inter-state coupling only at short times. For long times the bath-induced inter-state coupling is static and increases with the contribution of bath modes to the Stokes shift and to the Herzberg-Teller correction of the excited state. Simultaneously, the time evolution of excited state population is studied numerically for the system consisting of two electronic levels interacting with two vibrational modes, coupled to a heat bath. A mutual coupling of the vibrational modes in the excited state is taken into account (Duschinsky effect). Excited state population relaxes faster if interacting vibrational mode dissipates its energy via vibrational mode of a smaller eigenfrequency. Fast component of excited state depopulation cannot be achieved via coherent mode-mode coupling, if the second mode is not directly coupled to the electronic inter-state transition.