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Semiconducting MXenes are an intriguing two-dimensional (2D) material class with promising electronic and optoelectronic properties. Here, we focused on recently prepared Hf-based MXenes, namely, Hf3C2O2 and Hf2CO2. Using the first-principles calculation and excited state corrections, we proved their dynamical stability, reconciled their semiconducting behavior, and obtained fundamental gaps by using the many-body GW method (indirect 1.1 and 2.2 eV; direct 1.4 and 3.5 eV). Using the Bethe–Salpeter equation, we subsequently provided optical gaps (0.9 and 2.7 eV, respectively), exciton binding energies, absorption spectra, and other properties of excitons in both Hf-based MXenes. The indirect character of both 2D materials further allowed for a significant decrease of excitation energies by considering indirect excitons with exciton momentum along the Γ-M path in the Brillouin zone. The first bright excitons are strongly delocalized in real space while contributed by only a limited number of electron–hole pairs around the M point in the k-space from the valence and conduction band. A diverse range of excitonic states in Hf3C2O2 MXene lead to a 4% and 13% absorptance for the first and second peaks in the infrared region of absorption spectra, respectively. In contrast, a prominent 28% absorptance peak in the visible region appears in Hf2CO2 MXene. Results from radiative lifetime calculations indicate the promising potential of these materials in optoelectric devices requiring sustained and efficient exciton behavior. [ABSTRACT FROM AUTHOR]

We present a detailed theoretical analysis of polarized absorption spectra and linear dichroism of cyanine dye aggregates whose unit cells contain two molecules. The studied threadlike ordered system with a molecular exciton delocalized along its axis can be treated as two chains of conventional molecular aggregates, rotated relative to each other at a certain angle around the aggregate axis. Our approach is based on the general formulas for the effective cross section of light absorption by a molecular aggregate and key points of the molecular exciton theory. We have developed a self-consistent theory for describing the orientational effects in the absorption and dichroic spectra of such supramolecular structures with nonplanar unit cell. It is shown that the spectral behavior of such systems exhibits considerable distinctions from that of conventional cyanine dye aggregates. They consist in the strong dependence of the relative intensities of the J- and H-type spectral bands of the aggregate with a nonplanar unit cell on the angles determining the mutual orientations of the transition dipole moments of constituting molecules and the aggregate axis as well as on the polarization direction of incident light. The derived formulas are reduced to the well-known analytical expressions in the particular case of aggregates with one molecule in the unit cell. The calculations performed within the framework of our excitonic theory combined with available vibronic theory allow us to quite reasonably explain the experimental data for the pseudoisocyanine bromide dye aggregate. [ABSTRACT FROM AUTHOR]

Transient absorption (TA) spectroscopy of semiconductor nanocrystals (NCs) is often used for excited state population analysis, but recent results suggest that TA bleach signals associated with multiexcitons in NCs do not scale linearly with exciton multiplicity. In this manuscript, we probe the factors that determine the intensities and spectral positions of exciton and biexciton components in the TA spectra of CdSe quantum dots (QDs) of five diameters. We find that, in all cases, the peak intensity of the biexciton TA spectrum is less than 1.5 times that of the single exciton TA spectrum, in stark contrast to a commonly made assumption that this ratio is 2. The relative intensities of the biexciton and exciton TA signals at each wavelength are determined by at least two factors: the TA spectral intensity and the spectral offset between the two signals. We do not observe correlations between either of these factors and the particle diameter, but we find that both are strongly impacted by replacing the native organic surface-capping ligands with a hole-trapping ligand. These results suggest that surface trapping plays an important role in determining the absolute intensities of TA features for CdSe QDs and not just their decay kinetics. Our work highlights the role of spectral offsets and the importance of surface trapping in governing absolute TA intensities. It also conclusively demonstrates that the biexciton TA spectra of CdSe QDs at the band gap energy are less than twice as intense as those of the exciton. [ABSTRACT FROM AUTHOR]

Electroabsorption (EA) measurements can be used to identify the type of excitons contributing to the absorption spectra of semiconductors. However, the shape of the EA spectrum may vary depending on the mode of measurement due to the optical interference effects. Analysis without considering these effects may lead to erroneous conclusions. In this work, we present EA measurements and analysis for reflection mode measurements considering optical interference effects. We compared the inferences with transmission mode measurements and discuss the limitations. We identified the nature of excitons associated with each transition in the absorption spectrum of poly[(2,5-bis(2-hexyldecyloxy)-phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c]-[1,2,5]-thiadiazole)] thin film from EA measurements. The bands at 1.89, 2.05, and 2.27 eV had a mixed nature consisting of charge transfer and Frenkel characteristics. Of these, the band at 2.05 eV showed the strongest charge transfer characteristic. From thickness dependent measurements, we showed that the interference effects increase with the thickness of the semiconductor layer. The nature of excitons, however, could still be deduced qualitatively from reflection mode EA measurements. [ABSTRACT FROM AUTHOR]

The optoelectronic properties of quantum confined semiconductor nanocrystals depend critically on the band edge electron and hole levels and their exciton fine structures. Transient absorption (TA) spectroscopy has been widely used to probe the dynamics of photogenerated electrons, holes, and excitons in these materials through their state filling induced bleach of the band edge exciton transition. Such effects, in principle, reflect the band edge fine structures and are well understood for the conduction band electrons. However, the valence band hole state filling signals remain poorly understood due to the complexity of the valence band level structure and the presence of fast hole trapping in many materials. Herein, we report a study of the valence band hole state filling effect by comparing the TA spectra of CdSe quantum dots (QDs) with different degrees of hole trapping and by selective removal of the conduction band electrons to adsorbed methyl viologen molecules. We observe that in CdSe/CdS core/shell QDs with a high photoluminescence quantum yield of 81%, the valence band hole contributes to 22% ± 1% of the exciton bleach, while a negligible hole state filling signal is observed in CdSe core only QDs with a photoluminescence quantum yield of 17%. This hole state filling effect can be explained by a simplified valence band edge hole model that contains two sets of twofold degenerate hole levels that are responsible for the higher energy bright exciton and lower energy dark exciton states, respectively. Our result clarifies the TA spectral features of the valence band holes and provides insights into the nature of single hole states in CdSe-based QDs. [ABSTRACT FROM AUTHOR]

We theoretically propose a hybrid nanomechanical resonator (NR) system, where a doubly clamped suspended NR with an embedded quantum dot driven by two-tone fields is coupled to another NR via the Coulomb interaction, and we investigate the absorption spectra of the probe field under different exciton-pump field detuning. In the condition of pump on-resonance, the absorption spectrum gives a method to determine the coupling strength of the two NRs. In the pump off resonance, the absorption spectra exhibit double-Fano resonance, which is determined by the interaction of the two NRs, the frequencies of the two NRs, as well as the pump detuning. Furthermore, the double-Fano resonances are accompanied by the rapid normal phase dispersion, which indicates the slow- and fast-light effect. The results show that the group velocity index is tunable by the interaction of the two NRs, the detuning, and the different resonator frequencies, which can achieve the conversion from fast light to slow light. [ABSTRACT FROM AUTHOR]

Due to the exceptional photophysical properties and great potential applications in solid state lighting, zero-dimensional halide perovskites with broadband emitting have recently attracted much attention. In this work, to reveal the origin of the broadband absorption and emission spectra of 0D (C 4 N 2 H 14 Br) 4 SnBr x I 6 − x (x = 3), the ground state and exciton dynamics properties have been studied by hybrid PBE0 functional and the GW+BSE method. Different self-trapped excitons (STEs) are obtained, and their emission energies by PBE0 are consistent well with experimental data. By considering the vibrational broadening of emission, our calculated full width at half maximum of emission accords well with the experiment. The absorption of free exciton and STEs is also calculated by considering the quasiparticle and excitonic effect. Our results show that these light-induced trapped states can be observed by experiments, as confirmed in other similar systems by the femtosecond transient absorption spectra. [ABSTRACT FROM AUTHOR]

The absorption spectra of thin films (CsCl)1–x(CuCl)x were studied at T = 90 K in the spectral range 2–6 eV. From the analysis of the spectra, the formation of CsCu2Cl3 and Cs2CuCl3 compounds in the CsCl–CuCl system was created. The Cs2CuCl3 compound is stable only in a vacuum; in air, it apparently decomposes into CsCu2Cl3 with a disordered crystal lattice and CsCl. The exciton spectrum of both compounds is interpreted on the basis of transitions in the Cu+ ion. The one-dimensional character of excitons in CsCu2Cl3 and the two-dimensional character in Cs2CuCl3 were established. [ABSTRACT FROM AUTHOR]

Recently, interlayer and intralayer excitons in transition metal dichalcogenide heterobilayers have been studied both experimentally and theoretically. In spite of a growing interest, these layer-resolved excitons in the presence of external stimuli, such as strain, remain not fully understood. Here, using density-functional theory calculations with many-body effects, we explore the excitonic properties of vertically stacked MoSe2/WSe2 heterobilayer in the presence of in-plane biaxial strain of up to 5%. We calculate the strain dependence of exciton absorption spectrum, oscillator strength, wave function, and binding energy by solving the Bethe–Salpeter equation on top of the standard GW approach. We identify the interlayer and intralayer excitons by analyzing their electron-hole weights and spatial wave functions. We show that with the increase in strain magnitude, the absorption spectrum of the interlayer and intralayer excitons is red-shifted and re-ordered, and the binding energies of these layer-resolved excitons decrease monotonically and almost linearly. We derive the sensitivity of exciton binding energy to the applied strain and find that the intralayer excitons are more sensitive to strain than the interlayer excitons. For instance, a sensitivity of −7.9 meV/% is derived for the intra-MoSe2-layer excitons, which is followed by −7.4 meV/% for the intra-WSe2-layer excitons, and by −4.2 meV/% for the interlayer excitons. Our results indicate that interlayer and intralayer excitons in vertically stacked MoSe2/WSe2 heterobilayer are efficiently tunable by in-plane biaxial strain. [ABSTRACT FROM AUTHOR]

Vibrational-electronic (vibronic) resonance and its possible role in energy and charge transfer have been experimentally and theoretically investigated in several photosynthetic proteins. Using a dimer modeled on a typical photosynthetic protein, we contrast the description of such excitons provided by an exact basis set description, as opposed to a basis set with reduced vibrational dimensionality. Using a reduced analytical description of the full Hamiltonian, we show that in the presence of vibrational excitation both on electronically excited as well as unexcited sites, constructive interference between such basis states causes vibronic coupling between excitons to become progressively stronger with increasing quanta of vibrational excitation. This effect leads to three distinguishing features of excitons coupled through a vibronic resonance, which are not captured in basis sets that restrict ground state vibrations: (1) the vibronic resonance criterion itself, (2) vibronically assisted perfect delocalization between sites even though purely electronic mixing between the sites is imperfect due to energetic disorder, and (3) the nuclear distortion accompanying vibronic excitons becoming increasingly larger for resonant vibronic coupling involving higher vibrational quanta. In terms of spectroscopically observable limitations of reduced basis set descriptions of vibronic resonance, several differences are seen in absorption and emission spectra but may be obscured on account of overwhelming line broadening. However, we show that several features such as vibronic exciton delocalization and vibrational distortions associated with electronic excitations, which ultimately dictate the excited state wavepacket motions and relaxation processes, are fundamentally not described by basis sets that restrict ground state vibrations. [ABSTRACT FROM AUTHOR]

Photo-induced relaxation processes leading to excimer formations or other traps are in the focus of many investigations of optoelectronic materials because they severely affect the efficiencies of corresponding devices. Such relaxation effects comprise inter-monomer distortions in which the orientations of the monomer change with respect to each other, whereas intra-monomer distortions are variations in the geometry of single monomers. Such distortions are generally neglected in quantum chemical investigations of organic dye aggregates due to the accompanied high computational costs. In the present study, we investigate their relevance using perylene-bisimide dimers and diindenoperylene tetramers as model systems. Our calculations underline the importance of intra-monomer distortions on the shape of the potential energy surfaces as a function of the coupling between the monomers. The latter is shown to depend strongly on the electronic state under consideration. In particular, it differs between the first and second excited state of the aggregate. Additionally, the magnitude of the geometrical relaxation decreases if the exciton is delocalized over an increasing number of monomers. For the interpretation of the vibronic coupling model, pseudo-Jahn–Teller or Marcus theory can be employed. In the first part of this paper, we establish the accuracy of density functional theory-based approaches for the prediction of vibrationally resolved absorption spectra of organic semiconductors. These investigations underline the accuracy of those approaches although shortcomings become obvious as well. These calculations also indicate the strength of intra-monomer relaxation effects. [ABSTRACT FROM AUTHOR]

The vibrationally resolved absorption spectra of zinc phthalocyanine (ZnPc) aggregates (up to 70 monomers) are explored using the non-Markovian stochastic Schrödinger equation. Various types of local excitations, charge-transfer (CT) excitations, and exciton–phonon couplings are explicitly included in a comprehensive model Hamiltonian, which is parameterized by first-principles calculations. The absorption spectral simulations clarify that the two absorption bands in the Q-band region observed in experiments can be assigned to the contribution from the CT-mediated interactions, rather than the mixtures of different-type aggregates, as prevailingly assumed. Furthermore, the relative intensities of the two bands are found to be closely related to the intermolecular distance and molecular number in a ZnPc aggregate. From the investigation of the decoherence process after optical excitation, it is found that CT states can induce coherence regeneration as the time scale of charge separation is much faster than that of the vibration-induced decoherence. However, they would instead boost the decoherence process as the two time scales become comparable. The two different effects of CT states may suggest a novel way to regulate the decoherence process in excitation energy relaxation. [ABSTRACT FROM AUTHOR]

We study the exciton localization and resulting optical response for disordered tubular aggregates of optically active molecules. It has previously been shown that such tubular structures allow for excitons delocalized over more than a thousand molecules, owing to the combined effects of long-range dipole–dipole interactions and the higher-dimensional (not truly one-dimensional) nature of the aggregate. Such large delocalization sizes prompt the question to what extent in experimental systems the delocalization may still be determined by the aggregate size (diameter and length) and how this affects the aggregate's optical response and dynamics. We perform a systematic study of the size effects on the localization properties using numerical simulations of the exciton states in a cylindrical model structure inspired by the previously derived geometry of a cylindrical aggregate of cyanine dye molecules (C8S3). To characterize the exciton localization, we calculate the participation ratio and the autocorrelation function of the exciton wave function. We also calculate the density of states and absorption spectrum. We find strong effects of the tube's radius on the localization and optical properties in the range of parameters relevant to the experiment. In addition, surprisingly, we find that even for tubes as long as 750 nm, the localization size is limited by the tube's length for disorder values that are relevant to experimental circumstances, while observable effects of the tube's length in the absorption spectrum still occur for tube lengths up to about 150 nm. The latter may explain the changes in the optical spectra observed during the aging process of bromine-substituted C8S3 aggregates. For weak disorder, the exciton wave functions exhibit a scattered, fractal-like nature, similar to the quasi-particles in two-dimensional disordered systems. [ABSTRACT FROM AUTHOR]

The complex interplay between molecules and plasmonic metal nanoparticles (MNPs) presents a set of particular characteristics in absorption/scattering spectra such as excitonic splitting, asymmetric line shapes, plasmon-induced absorption enhancement and transparencies, etc. Although the MNP-molecule systems have been intensively investigated experimentally and theoretically, the construction of a theoretical framework which can produce all the disparate experimental observations and account for the electron-phonon (e-p) coupling is still in progress. Here, we present a theoretical approach which can account for both the plasmon-exciton coupling and the e-p interaction and produce all the spectral line shapes ranging from Fano antiresonance to Rabi splitting by simply tuning the coupling strength or plasmon damping rate. Additionally, we demonstrate the evolution of vibronic spectra and exciton dynamics with the coupling strength, plasmon damping rate, and detuning energy. It is found that the vibronic structures appearing in Rabi-like spectra are worse resolved, wider, and more largely shifted than those appearing in the Fano regime, attributed to the more significant deformation of the molecular vibrational wavepacket in the Rabi-like regime than that in the Fano regime as the molecular e-p interaction increases. The positive/negative value of detuning energy can induce different degrees of the vibrational wavepacket deformation and subsequently a different effect on the spectra in different coupling regimes. [ABSTRACT FROM AUTHOR]

A methodology is described to extract the absorption coefficient spectrum and exciton oscillator strength of GaN layers and GaN/AlGaN quantum wells by analyzing microtransmittance experiments in high-quality, free-standing membranes with thicknesses in the 160–230 nm range. The absorbance of a subwavelength GaN membrane is found to be an oscillating function of its thickness, in keeping with the standing wave effect. We analyze our results using two alternative models including interference effects and extract identical absorption coefficient values. The room-temperature absorption coefficient of bulk GaN membranes at the main exciton peak is found to be 9 × 104 cm−1. In the case of GaN/AlGaN quantum wells, the enhancement and blue shift of the excitonic absorption are observed, as a result of quantum confinement. [ABSTRACT FROM AUTHOR]

The photo-Hall-effect was applied to the study of electron dynamics in semi-insulating Fe-doped GaN. High-powered light-emitting diodes of wavelengths k = 940, 536, 449, 402, and 365 nm were used to excite steady-state free-electron volume concentrations Dn = 105 - 108cm-3, depending on k and intensity I0. Electron lifetime s was determined from the energy E dependence of the excited sheet electron concentration Dns through the relationship Dns = I0sA(E), where the absorbance A(E) is a known function of sample thickness d and absorption coefficient a, and the energy dependence of a is taken from a theory of deep-center photoionization. The major sample impurities were Fe, Si, and C, with [Fe] ⪢ [Si] and [C]. Fitted lifetimes s ranged from 15 to 170 ps, depending on [Fe]. It was found that Dns ∞ I0 for [Si]>[C] and ∞ I01/2 for [Si] < [C]; the latter dependence arises possibly from self-compensation of neutral C impurities by N-vacancy donors. For [Si] > [C], some of the neutral Fe3+ is converted to Fe2+ with ground state Fe2+(5E) and excited state Fe2+(5T2); a fit of n vs. temperature T over the range of 290-325K in the dark establishes E5E with respect to the conduction band: ECB - E5E = 0.564 eV-b5ET, where b5E = 3.6 × 10-4 eV/K. At room temperature, 294K, ECB - E5E = 0.46 eV and ECB - E5T2 = 0.07 eV. [ABSTRACT FROM AUTHOR]

In the present work, we accurately calculate the absorption spectrum of liquid ammonia up to 13 eV using many-body perturbation approach. The electronic bandgap of liquid NH3 is perfectly described as the combination of density functional theory, Coulomb-hole screened exchange, and G0W0 approximation to the electronic self-energy, yielding a direct gap (Γ→ Γ) of 7.71 eV, fully consistent with the experimentally measured gap from photo-emission spectroscopy. With respect to the NH3 optical properties, the entire spectrum in particular the low lying first absorption band is extremely affected by electron-hole interactions, leading to a fundamental redistribution of spectral weights of the independent-particle spectrum. Three well separated but broad main peaks are identified at 7.0, 9.8, and 11.8 eV with steadily increasing intensities in excellent agreement with the experimental data. Furthermore, we observe a giant net blue-shift of the first absorption peak of about 1.4 eV from gaseous to liquid phase as the direct consequence of many-body effects, allowing the associated liquid ammonia absorption band exciton to delocalize and feel more effectively the repulsion effects imposed by the surrounding solvent shells. Further, the spectrum is insensitive to the coupling of resonant and anti-resonant contributions. Concerning electronic response structure of liquid NH3, it is most sensitive to excitations at energies lower than its electronic gap. [ABSTRACT FROM AUTHOR]

In the present paper, accurate optical absorption spectrum of liquid H2O is calculated in the energy range of 5-20 eV to probe the nature of water's excited states by means of many body perturbation approach. Main features of recent inelastic X-ray measurements are well reproduced, such as a bound excitonic peak at 7.9 eV with a shoulder at 9.4 eV as well as the absorption maximum at 13.9 eV, followed by a broad shoulder at 18.4 eV. The spectrum is dominated by excitonic effects impacting the structures of the spectrum at low and higher energy regimes mixed by single particle effects at high energies. The exciton distribution of the low-energy states, in particular of S1, is highly anisotropic and localized mostly on one water molecule. The S1 state is essentially a HOCO-LUCO (highest occupied crystal orbital - lowest unoccupied crystal orbital) transition and of intra-molecular type, showing a localized valence character. Once the excitation energy is increased, a significant change in the character of the electronically excited states occurs, characterized through emergence of multiple quasi-particle peaks at 7.9 eV in the quasi-particle (QP) transition profile and in the occurring delocalized exciton density distribution, spread over many more water molecules. The exciton delocalization following a change of the character of excited states at around 7.9 eV causes the blue shift of the first absorption band with respect to water monomer S1. However, due to reduction of the electronic band gap from gas to liquid phase, following enhanced screening upon condensation, the localized S1 state of liquid water is red-shifted with respect to S1 state of water monomer. For higher excitations, near vertical ionization energy (11 eV), quasi-free electrons emerge, in agreement with the conduction band electron picture. Furthermore, the occurring red and blue shift of the excited states are independent of the coupling of resonant and anti-resonant contributions to the spectrum. [ABSTRACT FROM AUTHOR]

The absorption spectra of RbCu2Cl3 and Rb2Cu3Cl5 thin films were studied in the 2−6 eV spectral and 90−450 K temperature ranges. The localization of excitons in CuCl 4 3 − structural elements of crystal lattice of compounds, three-dimensional nature of excitons in RbCu2Cl3 and two-dimensional nature of excitons in Rb2Cu3Cl5 were established. The exciton spectra of RbCu2Cl3 and Rb2Cu3Cl5 thin films were interpreted based on the transitions in the Cu+ ion. [ABSTRACT FROM AUTHOR]

We have studied light matter interaction in quantum dot and exciton polaritonic coupler hybrid systems. The coupler is made by embedding two slabs of an excitonic material (CdS) into a host excitonic material (ZnO). An ensemble of non-interacting quantum dots is doped in the coupler. The bound exciton polariton states are calculated in the coupler using the transfer matrix method in the presence of the coupling between the external light (photons) and excitons. These bound exciton-polaritons interact with the excitons present in the quantum dots and the coupler is acting as a reservoir. The Schrödinger equation method has been used to calculate the absorption coefficient in quantum dots. It is found that when the distance between two slabs (CdS) is greater than decay length of evanescent waves the absorption spectrum has two peaks and one minimum. The minimum corresponds to a transparent state in the system. However, when the distance between the slabs is smaller than the decay length of evanescent waves, the absorption spectra has three peaks and two transparent states. In other words, one transparent state can be switched to two transparent states when the distance between the two layers is modified. This could be achieved by applying stress and strain fields. It is alsofound that transparent states can be switched on and off by applying an external control laser field. [ABSTRACT FROM AUTHOR]

We conduct polarization-dependent ultrafast spectroscopy to study the dynamics of singlet fission (SF) in tetracene single crystals. The spectrotemporal species for singlet and triplet excitons in transient absorption spectra are found to be strongly dependent on probe polarization. By carefully analyzing the polarization dependence, the signals contributed by different transitions related to singlet excitons have been disentangled, which is further applied to construct the correlation between dynamics of singlet and triplet excitons. The anisotropy of exciton dynamics provides an alternative approach to tackle the long-standing challenge in understanding the mechanism of singlet fission in organic semiconductors. [ABSTRACT FROM AUTHOR]

We extend our previous work on singlet exciton fission in isolated dimers to the case of crystalline materials, focusing on pentacene as a canonical and concrete example. We discuss the proper interpretation of the character of low-lying excited states of relevance to singlet fission. In particular, we consider a variety of metrics for measuring charge-transfer character, conclusively demonstrating significant charge-transfer character in the low-lying excited states. The impact of this electronic structure on the subsequent singlet fission dynamics is assessed by performing real-time master-equation calculations involving hundreds of quantum states. We make direct comparisons with experimental absorption spectra and singlet fission rates, finding good quantitative agreement in both cases, and we discuss the mechanistic distinctions that exist between small isolated aggregates and bulk systems. [ABSTRACT FROM AUTHOR]

We examine the excitonic properties of layered configurations of low dimensional transition metal dichalcogenides (LTMDCs) using the fractional dimensional space approach. The binding energies of the exciton, trion, and biexciton in LTMDCs of varying layers are analyzed, and linked to the dimensionality parameter α, which provides insight into critical electro-optical properties (relative oscillator strength, absorption spectrum, exciton-exciton interaction) of the material systems. The usefulness of α is highlighted by its independence of the physical mechanisms underlying the confinement effects of geometrical structures. Our estimates of the binding energies of exciton complexes for the monolayer configuration of transition metal dichalcogenides suggest a non-collinear structure for the trion and a positronium-molecule-like square structure for the biexciton. [ABSTRACT FROM AUTHOR]

The optical properties of an isolated firefly luciferin anion are investigated by using first-principles calculations, employing the many-body perturbation theory to take into account the excitonic effect. The calculated photoabsorption spectra are compared with the results obtained using the timedependent density functional theory (TDDFT) employing the localized atomic orbital (AO) basis sets and a recent experiment in vacuum. The present method well reproduces the line shape at the photon energy corresponding to the Rydberg and resonance excitations but overestimates the peak positions by about 0.5 eV. However, the TDDFT-calculated positions of some peaks are closer to those of the experiment. We also investigate the basis set dependency in describing the free electron states above vacuum level and the excitons involving the transitions to the free electron states and conclude that AO-only basis sets are inaccurate for free electron states and the use of a plane wave basis set is required [ABSTRACT FROM AUTHOR]

We explore the interaction between a quantum emitter and a metal nanoring by numerical solution of coupled Maxwell-Liouville equations. When the quantum emitter and nanoring are subjected to an incident plane wave, coupling between the quantum emitter and a dark plasmon supported by the nanoring gives rise to a similar lineshape to the familiar Fano type. It results from the excitation of a dark plasmon via intermediary participation of the quantum emitter. The dark plasmon is characterized through the width and shift parameters of the emitter peak in the absorption spectrum of the nanoparticle. Our results are obtained with the help of finite-difference time-domain method and a recently proposed symmetry-adapted averaging approach. [ABSTRACT FROM AUTHOR]

This paper reports on the defect correlated self-quenching and spectroscopic investigation of calcium titanate (CaTiO3) phosphors. A series of CaTiO3 phosphors doped with trivalent europium (Eu3+) and codoped with potassium (K+) ions were prepared by the solid state reaction method. The X-ray diffraction results revealed that the obtained powder phosphors consisted out of a single-phase orthorhombic structure and it also indicated that the incorporation of the dopants/co-dopants did not affect the crystal structure. The scanning electron microscopy images revealed the irregular morphology of the prepared phosphors consisting out of lm sized diameter particles. The Eu3+ doped phosphors illuminated with ultraviolet light showed the characteristic red luminescence corresponding to the 5D0→7Fj transitions of Eu3+. As a charge compensator, K+ ions were incorporated into the CaTiO3:Eu3+ phosphors, which enhanced the photoluminescence (PL) intensities depending on the doping concentration of K+. The concentration quenching of Eu3+ in this host is discussed in the light of ion-ion interaction, electron phonon coupling, and defect to ion energy transfer. The spectral characteristics and the Eu-O ligand behaviour were determined using the Judd-Ofelt theory from the PL spectra instead of the absorption spectra. The CIE (International Commission on Illumination) parameters were calculated using spectral energy distribution functions and McCamy's empirical formula. Photometric characterization indicated the suitability of K+ compensated the CaTiO3:Eu3+ phosphor for pure red emission in light-emitting diode applications. [ABSTRACT FROM AUTHOR]

We report the detailed balance analysis of the photovoltaic conversion efficiency of nanocrystal solar cells with discrete excitonic absorption profiles. We calculated the conversion efficiency limits of single junction, multiexciton, and tandem solar cells as a function of exciton peak energy and width. We delineate the width of the absorption spectrum in terms of the energetic width of an isolated nanocrystal and the physical width due to the nanocrystal diameter distribution in the ensemble. Our results suggest that the conversion efficiency is less strongly impacted by the ensemble distribution than by the energetic peak width. [ABSTRACT FROM AUTHOR]

The geometry and infrared absorption spectrum of (RbCs)2 have been studied by full dimensional quantum dynamics simulations. For this purpose, the potential energy and dipole moment surfaces are generated by means of a cluster expansion with all two and three mode correlations, and fitted to analytical expressions with negligible deviations. Accordingly, the ground state (RbCs)2 has a diamond geometry with D2h symmetry. The infrared spectrum with frequencies up to 120 cm-1, exhibits rich details of the fundamentals, overtones, and combination bands; the highest fundamental frequency of (RbCs)2 is only 40.26 cm-1. The present study unravels important details of the interactions between the widely investigated ultracold RbCs molecules. [ABSTRACT FROM AUTHOR]

In this work, we present measurements of the dynamics of photoexcited carriers in GaInN/GaN quantum wells (QWs) grown on ammonothermal GaN, especially thermalization and recombination rates. Emission properties were measured by time-resolved photoluminescence (PL) and electroluminescence spectroscopy. Due to the use of high quality homoepitaxial material, we were able to obtain very valuable data on carrier thermalization. The temperature dependence of the QW energy observed in PL shows characteristic S-shape with a step of about 10 meV. Such a behavior (related to thermalization and localization at potential fluctuations) is often reported for QWs; but in our samples, the effect is smaller than in heteroepitaxial InGaN/GaN QWs due to lower potential fluctuation in our material. Absorption properties were studied by photocurrent spectroscopy measurements. A comparison of emission and absorption spectra revealed a shift in energy of about 60 meV. Contrary to PL, the QW energy observed in absorption decreases monotonically with temperature, which can be described by a Bose-like dependence E(T) = E(0) - λ/(exp(θ/T) - 1), with parameters λ = (0.11 ± 0.01) eV, θ = (355 ± 20) K, or by a Varshni dependence with coefficients α = (10 ± 3) × 10-4 eV/K and β = (1500 ± 500) K. Taking into account absorption and emission, the fluctuation amplitude (according to Eliseev theory) was σ = 14 meV. The time resolved PL revealed that in a short period (<1 ns) after excitation, the PL peaks were broadened because of the thermal distribution of carriers. We interpreted this distribution in terms of quasi-temperature (Tq) of the carriers. The initial Tq was of the order of 500 K. The thermalization led to a fast decrease of Tq. The obtained cooling time in the QW was τC = 0.3 ns, which was faster than the observed recombination time τR = 2.2 ns (at 4 K). [ABSTRACT FROM AUTHOR]

Frequency dependent absorption by materials at distinct frequencies in the THz range is commonly used as spectral-fingerprints for identification and classification. For transmission measurements, the substance under study is often mixed with a transparent host material. Refractive index variations arising from the presence of impurities and inconsistencies in the sample's internal structure often cause the incident radiation to scatter. This can significantly distort the measured spectral-fingerprints. In this letter, we present a numerical approach to allay the scattering contribution in THz-TDS measurements, provided the sample's refractive index is known, and reveal the true absorption spectra for a given sample. [ABSTRACT FROM AUTHOR]

The band structure and optical absorption spectrum of lithium peroxide (Li2O2) is calculated from first-principles using the G0W0 approximation and the Bethe-Salpeter equation, respectively. A strongly localized (Frenkel type) exciton corresponding to the π*→σ* transition on the O2-2 peroxide ion gives rise to a narrow absorption peak around 1.2 eV below the calculated bandgap of 4.8 eV. In the excited state, the internal O2-2 bond is significantly weakened due to the population of the σ* orbital. As a consequence, the bond is elongated by almost 0.5 Å leading to an extreme Stokes shift of 2.6 eV. The strong vibronic coupling entails significant broadening of the excitonic absorption peak in good agreement with diffuse reflectance data on Li2O2 which shows a rather featureless spectrum with an absorption onset around 3.0 eV. These results should be important for understanding the origin of the high potential losses and low current densities, which are presently limiting the performance of Li-air batteries. [ABSTRACT FROM AUTHOR]

We investigate theoretically the phenomenon of exchange narrowing in the absorption spectrum of a chain of monomers, which are coupled via resonant dipole-dipole interaction. The individual (uncoupled) monomers exhibit a broad absorption line shape due to the coupling to an environment consisting of a continuum of vibrational modes. Upon increasing the interaction between the monomers, the absorption spectrum of the chain narrows. For a non-Markovian environment with a Lorentzian spectral density, we find a narrowing of the peak width [full width at half maximum (FWHM)] by a factor 1/N, where N is the number of monomers. This is much stronger than the usual [formula] narrowing. Furthermore, it turns out that for a Markovian environment no exchange narrowing at all occurs. The relation of different measures of the width (FWHM, standard deviation) is discussed. [ABSTRACT FROM AUTHOR]

We report experimental and theoretical studies of the two-photon absorption spectrum of two nitrofuran derivatives: nitrofurantoine, (1-(5-nitro-2-furfurilideneamine)-hidantoine) and quinifuryl, 2-(5′-nitro-2′-furanyl)ethenyl-4-{N-[4′-(N,N-diethylamino)-1′-methylbutyl]carbamoyl} quinoline. Both molecules are representative of a family of 5-nitrofuran-ethenyl-quinoline drugs that have been demonstrated to display high toxicity to various species of transformed cells in the dark. We determine the two-photon absorption cross-section for both compounds, from 560 to 880 nm, which present peak values of 64 GM for quinifuryl and 20 GM for nitrofurantoine (1 GM = 1×10-50cm4.s.photon-1). Besides, theoretical calculations employing the linear and quadratic response functions were carried out at the density functional theory level to aid the interpretations of the experimental results. The theoretical results yielded oscillator strengths, two-photon transition probabilities, and transition energies, which are in good agreement with the experimental data. A higher number of allowed electronic transitions was identified for quinifuryl in comparison to nitrofurantoine by the theoretical calculations. Due to the planar structure of both compounds, the differences in the two-photon absorption cross-section values are a consequence of their distinct conjugation lengths. [ABSTRACT FROM AUTHOR]

The high-frequency region was used to record the absorption spectrum of water in nanoscale pores during vacuum pumping or injection of water. The wide spectral range, which included the vibration overtones, allowed to resolve the structure of the absorption bands with variation of water concentration in the pores of SiO2. The absorption bands of water clusters in the 4570-5400 cm-1 range consist of well-resolved sub-bands with interpeak intervals of up to 580 cm-1. When the pore diameter is decreased from 11.8 to 2.6 nm, the absorption bands of clusters in this frequency range are shifted by 530 cm-1 in the direction of the water monomer which indicates an increase of hydrogen bond strength in confined water with an increase of the pore diameter. The spectrum recorded during water pumping is extremely variable in time, and the cluster dynamics in large pores (11.8 nm) differs greatly from the dynamics in small pores (2.6 nm). While all types of water clusters are removed from small pores uniformly, in the case of large pores, the water clusters relating to strong hydrogen bonds are removed from the sample at the beginning of the vacuum pumping and the loosely coupled clusters are removed later. The rate of this process is not steady and varies throughout pumping. [ABSTRACT FROM AUTHOR]

Absorption and linear dichroism spectra of self-assembled tubular aggregates of TPPS4 porphyrin are studied theoretically with special emphasis on the low energy part of the spectra (the Q band region) where the coupling with intramolecular vibrations is pronounced. The model Hamiltonian includes both the excitonic coupling between four molecular electronic excited states contributing to the porphyrin Q and B bands as well as the intermediate-strength linear exciton-phonon coupling to one effective high-frequency molecular vibrational mode. Good agreement between the calculated and experimental spectra is obtained. The results allow us to identify the nature of the peaks observed in the Q band region of the aggregate’s absorption spectrum; we show that the two most prominent peaks within the Q band originate from two different excitonic subbands. It is shown that the coupling between the Q and B bands plays an important role and the vibronic coupling affects the details of the absorption lineshape. [ABSTRACT FROM AUTHOR]

We present ultrafast transient absorption spectra of two oligofluorene derivatives in dilute solution. These spectra display a photoinduced absorption band with clear vibronic structure, which we analyze rigorously using a time-dependent formalism of absorption to extract the principal excited-state vibrational normal-mode frequencies that couple to the electronic transition, the configurational displacement of the higher-lying excited state, and the reorganization energies. We can model the excited-state absorption spectrum using two totally symmetric vibrational modes with frequencies 450 (dimer) or 400 cm-1 (trimer), and 1666 cm-1. The reorganization energy of the ground-state absorption is rather insensitive to the oligomer length at 230 meV. However, that of the excited-state absorption evolves from 58 to 166 meV between the oligofluorene dimer and trimer. Based on previous theoretical work [A. Shukla et al., Phys. Rev. B 67, 245203 (2003)], we assign the absorption spectra to a transition from the 1Bu excited state to a higher-lying mAg state, and find that the energy of the excited-state transition with respect to the ground-state transition energy is in excellent agreement with the theoretical predictions for both oligomers studied here. These results and analysis permit profound understanding of the nature of excited-state absorption in π-conjugated polymers, which are the subject of general interest as organic semiconductors in the solid state. [ABSTRACT FROM AUTHOR]

The electronic excitation energies and transition dipole moments are the essential ingredients to compute an optical spectrum of any molecular system. Here we extend the exciton scattering (ES) approach, originally developed for computing excitation energies in branched conjugated molecules, to the calculation of the transition dipole moments. The ES parameters that characterize contributions of molecular building blocks to the total transition dipole can be extracted from the quantum-chemical calculations of the excited states in simple molecular fragments. Using these extracted parameters, one can then effortlessly calculate the oscillator strengths and optical spectra of various large molecular structures. We illustrate application of this extended ES approach using an example of phenylacetylene-based molecules. Absorption spectra predicted by the ES approach show close agreement with the results of the reference quantum-chemical calculations. [ABSTRACT FROM AUTHOR]

The Ã-X electronic absorption spectrum of vinoxy radical has been investigated using room temperature cavity ringdown spectroscopy. Analysis of the observed bands on the basis of computed vibrational frequencies and rotational envelopes reveals that two distinct types of features are present with comparable intensities. The first type corresponds to “normal” allowed electronic transitions to the origin and symmetric vibrations in the à state. The second type is interpreted in terms of excitations to asymmetric à state vibrations, which are only vibronically allowed by Herzberg–Teller coupling to the B state. Results of electronic structure calculations indicate that the magnitude of the Herzberg–Teller coupling is appropriate to produce vibronically induced transitions with intensities comparable to those of the normal bands. [ABSTRACT FROM AUTHOR]

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of CH3CO and O2; IR absorption spectra of CH3C(O)OO and α-lactone were observed. Absorption bands with origins at 1851±1, 1372±2, 1169±6, and 1102±3 cm-1 are attributed to t-CH3C(O)OO, and those at 1862±3, 1142±4, and 1078±6 cm-1 are assigned to c-CH3C(O)OO. A weak band near 1960 cm-1 is assigned to α-lactone, cyc-CH2C(==O)O, a coproduct of OH. These observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters and dipole derivatives, and observed vibrational wavenumbers agree with harmonic vibrational wavenumbers predicted with B3LYP/aug-cc-pVDZ density-functional theory. The observed relative intensities indicate that t-CH3C(O)OO is more stable than c-CH3C(O)OO by 3±2 kJ mol-1. Based on these observations, the branching ratio for the OH+α-lactone channel of the CH3CO+O2 reaction is estimated to be 0.04±0.01 under 100 Torr of O2 at 298 K. A simple kinetic model is employed to account for the decay of CH3C(O)OO. [ABSTRACT FROM AUTHOR]

The approximate quantum mechanical ring polymer molecular dynamics (RPMD) and linearized semiclassical initial value representation (LSC-IVR) methods are compared and contrasted in a study of the dynamics of the flexible q-TIP4P/F water model at room temperature. For this water model, a RPMD simulation gives a diffusion coefficient that is only a few percent larger than the classical diffusion coefficient, whereas a LSC-IVR simulation gives a diffusion coefficient that is three times larger. We attribute this discrepancy to the unphysical leakage of initially quantized zero point energy (ZPE) from the intramolecular to the intermolecular modes of the liquid as the LSC-IVR simulation progresses. In spite of this problem, which is avoided by construction in RPMD, the LSC-IVR may still provide a useful approximation to certain short-time dynamical properties which are not so strongly affected by the ZPE leakage. We illustrate this with an application to the liquid water dipole absorption spectrum, for which the RPMD approximation breaks down at frequencies in the O–H stretching region owing to contamination from the internal modes of the ring polymer. The LSC-IVR does not suffer from this difficulty and it appears to provide quite a promising way to calculate condensed phase vibrational spectra. [ABSTRACT FROM AUTHOR]

Absorption spectra of hexa-peri-hexabenzocoronene isolated in rare-gas matrices are reported for the wavelength range between 200 and 500 nm. Measurements were carried out in neon and in argon at 5.8 and 12.0 K, respectively. Calculations based on semiempirical models and on density-functional theory were performed to assign the observed features. The electronically excited states involved in Clar’s α- and p-bands are identified as S1(B2u) and S2(B1u), respectively. Although the upper state associated with the β-band is found to be a 1E1u state, it remains undetermined whether it is S3 or S4. Structures in the β-band are interpreted as resulting from the interaction between the 1E1u state and the e2g vibrational manifold of S2(B1u). The new measurements are used to narrow down the wavelength ranges where the bands of hexa-peri-hexabenzocoronene should be found in the gas phase. A previous estimate of the interstellar abundance of this polycyclic aromatic hydrocarbon is discussed. [ABSTRACT FROM AUTHOR]

Fundamental optical and structural properties of melanins are not well understood due to their poor solubility characteristics and the chemical disorder present during biomolecular synthesis. We apply nonlinear transient absorption spectroscopy to quantify molar absorptivities for eumelanin and pheomelanin and thereby get an estimate for their average pigment sizes. We determine that pheomelanin exhibits a larger molar absorptivity at near IR wavelengths (750 nm), which may be extended to shorter wavelengths. Using the molar absorptivities, we estimate that melanin pigments contain ∼46 and 28 monomer units for eumelanin and pheomelanin, respectively. This is considerably larger than the oligomeric species that have been recently proposed to account for the absorption spectrum of eumelanin and illustrates that larger pigments comprise a significant fraction of the pigment distribution. [ABSTRACT FROM AUTHOR]

Zn0.95-xCo0.05LixO (x=0–0.12) thin films were synthesized by sol-gel method. Magnetic investigation showed that the ferromagnetism of the Zn0.95-xCo0.05LixO films increased with Li doping within the solubility limit of 9% but dropped sharply when x>9% owing to the presence of the second-phase LiCoO2. X-ray diffraction, UV-visible absorption spectrum (UV-vis), Raman spectrum (Raman), and electrical resistivity investigation indicated that the Li-doping process in Zn0.95Co0.05O was of three stages. The structure and magnetic properties of Zn0.95-xCo0.05LixO films had different change trends in different stages. It was found that not only LiZn′ related defects but also Li+ interstitials played important roles in enhancing the magnetic interaction between Co2+ ions, which was supported by the bound magnetic polaron model. [ABSTRACT FROM AUTHOR]

Luminescence enhancement and quenching of Eu(TTA)3·2H2O complex in DMF (N,N-dimethylformamide) solution containing silver nanoparticles were observed, which depended on the concentrations of both europium complex and silver nanoparticles. Their origins were discussed based on absorption spectra, excitation and emission spectra, and luminescent decay dynamics. The results indicated that when the concentration of Eu complex was high enough, strong interaction among complex molecules occurred. The presence of Ag nanoparticles definitely decreased the interaction among complex molecules. In the solution containing Ag nanoparticles the electronic-dipole transition rate of 5D0-7F2 increased due to enhanced local field surrounding Eu3+ ions, while the nonradiative transition rate from 5D0 decreased owing to decreased resonant energy transfer among europium complex molecules. These two factors lead to the luminescence enhancement of europium complex. As to the luminescent quenching, was attributed to absorption competition between Ag nanoparticles and europium complex at excited wavelength. [ABSTRACT FROM AUTHOR]

The laser-induced fluorescence spectra (both fluorescence excitation and dispersed fluorescence) of jet-cooled 1,3-benzodioxan along with its ultraviolet absorption spectra have been recorded and analyzed in order to determine the vibrational quantum levels in both the ground and S1(π,π*) electronic excited states. A detailed energy map of the vibrational levels involving the six lowest frequency vibrations was established and utilized to better understand the structural and conformational differences between the ground and excited electronic states. The energies of more than a dozen vibrational excited states involving the out-of-plane ring twisting (ν47) and the out-of-plane ring bending (ν48) modes were determined for both S0 and S1 electronic states. Ab initio and density functional theory (DFT) calculations were also carried out to complement the experimental work. The data allowed one-dimensional potential energy functions in terms of the ring-twisting coordinate to be calculated. These show the molecule to have a twisting angle of 33° and a barrier to planarity of 4300±500 cm-1 for the S0 ground state and an angle of 24° and a barrier of 1500±200 cm-1 for the S1(π,π*) excited state. [ABSTRACT FROM AUTHOR]

A general formalism for introducing nuclear quantum effects in the expression of the quantum time correlation function of an operator in a multilevel electronic system is presented in the adiabatic limit. The final formula includes the nuclear quantum time correlation functions of the operator matrix elements, of the energy gap, and their cross terms. These quantities can be inferred and evaluated from their classical analogs obtained by mixed quantum-classical molecular dynamics simulations. The formalism is applied to the absorption spectrum of a hydrated electron, expressed in terms of the time correlation function of the dipole operator in the ground electronic state. We find that both static and dynamic nuclear quantum effects distinctly influence the shape of the absorption spectrum, especially its high energy tail related to transitions to delocalized electron states. Their inclusion does improve significantly the agreement between theory and experiment for both the low and high frequency edges of the spectrum. It does not appear sufficient, however, to resolve persistent deviations in the slow Lorentzian-like decay part of the spectrum in the intermediate 2–3 eV region. [ABSTRACT FROM AUTHOR]

Pyrylium dyes having the same basic chemical structure, differing only to a specific substituent, have been used as novel materials for multiphoton three-dimensional data storage. Electronic absorption spectra, two-photon and three-photon absorption properties of this class of pyrylium dyes, have been studied theoretically and compared to experimental results. The effects of the counteranion, the surrounding solvent, and electron releasing and electron withdrawing groups in specific positions of the basic structure have been explored in detail. It is argued that on grounds of the quality of experimental spectroscopic agreement, the computed two- and three-photon data may be used in pulse propagation simulations of three-dimensional recording in optical memories. [ABSTRACT FROM AUTHOR]

Dilute-nitride GaNSb bulk materials with up to 1.4% nitrogen were grown by molecular beam epitaxy on GaSb substrates. Hall measurements indicate residual hole concentrations of nearly 1019 cm-3 at room temperature, but a decrease to below 1016 cm-3 and a hole mobility of 1300 cm2/V s at 4.5 K for a sample with 0.6% nitrogen. Photoluminescence (PL) and optical absorption measurements demonstrate a bandgap reduction by up to 300 meV with increasing nitrogen incorporation. The experimental absorption spectra are well fit by a functional dependence corresponding to direct allowed optical transitions, and the PL spectra are also consistent with that interpretation. Room temperature carrier relaxation times in the picosecond range are measured using an ultrafast PL upconversion technique. [ABSTRACT FROM AUTHOR]

We present a joint theoretical and experimental investigation of the absorption spectra of silver clusters Agn (4≤n≤22). The experimental spectra of clusters isolated in an Ar matrix are compared with the calculated ones in the framework of the time-dependent density functional theory. The analysis of the molecular transitions indicates that the s-electrons are responsible for the optical response of small clusters (n≤8) while the d-electrons play a crucial role in the optical excitations for larger n values. [ABSTRACT FROM AUTHOR]

The evolution of the frequency-dependent absorption spectra for plastoferrites and carbon black-filled ethylene butylacrylate copolymer composites subjected to a uniaxial tension is evaluated using a vector network analyzer as a function of the elongation ratio over the frequency range of 0.3–5 GHz and at room temperature. The absorption spectrum has a double-peaked structure with two broad and symmetrical components. The positions of the lower-frequency peak (1.5 GHz) and the higher-frequency (≅4±0.3 GHz) do not change with extension over the considered range of strain, however, their relative absorption energy changes versus tensile stress can be explained in terms of a Gaussian molecular network model (affine behavior) provided that the elasticity network in the material occurs in a manner that is topologically similar to the elasticity network of a conventional rubber. The sensitivity of the microwave absorption to elongation ratio can be exploited to provide artificially structured materials with tunable electromagnetic properties. [ABSTRACT FROM AUTHOR]