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The plasmonic coupling between silver (Ag) and gold (Au) nanoparticles (NPs) under four polarization modes was examined: a longitudinal mode (L-mode), where the electric field of a linearly polarized incident light parallels the dimer axis, and three transverse modes (T-modes), where the electric field of the light is perpendicular to the dimer axis. The coupling was studied using the discrete dipole approximation followed by an in-house postprocessing code that determines the extinction (Qext), absorption (Qabs), and near-field (Qnf) spectra from the individual NPs as well as the whole system. In agreement with the literature results, the extinction/absorption spectra of the whole dimer have two peaks, one near the Ag localized surface plasmon resonance (LSPR) region and the other at the Au LSPR region, with the peak at Ag LSPR being reduced in all modes and the peak at Au LSPR being red-shifted and increased in the L-mode but not in the T-modes. It is further shown that the scattering at the Ag LSPR region is reduced and becomes less than the isolated Ag NPs, but the absorption at the Ag LSPR is increased and becomes greater than the isolated Ag NPs for the 50 nm Ag–Au heterodimer. This suggests that the scattering from Ag NPs is being reabsorbed by the neighboring Au NPs due to the interband electronic transition in Au at that wavelength range. The Qext from the individual NP in the heterodimer shows the presence of the Fano profile on the Au NP but not on the Ag NP. This phenomenon was further investigated by using a dielectric particle (DP) placed near the Ag or Au NPs. The Fano profile appears in the absorbing DP spectra placed near either Ag or Au NPs. However, the Fano profile is masked upon further increases in the refractive index value of the DP particle. This explains the absence of a Fano profile on the Ag NPs in the Ag–Au heterodimer. The large near-field enhancement on both Ag and Au NPs at the Au plasmonic wavelength in the L-mode for large NPs was investigated through a DP-Au system. The large enhancement was shown to arise from a large imaginary component of the DP refractive index and a small real component. Through examination of both the near- and far-field properties of the individual NPs as well as the whole system and examinations of DP-Ag and DP-Au systems, our study provides a new understanding of the couplings between Ag and Au NPs. [ABSTRACT FROM AUTHOR]

A high-resolution absorption spectrum of the S1–S0 transition of free-base phthalocyanine was observed and analyzed with improved reliability. The spectrum, with a partially resolved rotational structure, was obtained by using the buffer-gas cooling technique and a single-mode tunable laser. Our new analysis reveals that the S 1 ← S 0 0 0 0 band belongs to the a-type transition, where the electronic transition moment aligns parallel to the NH–HN direction, allowing the assignment of the S1 state to 1B3u. These results agree with a prior study using supersonic expansion and are well supported by theoretical calculations. Interestingly, the rotational constant B in the S1 state, which is often smaller than that in the ground state for typical molecules, was found to be slightly larger than that in the S01Ag state. This suggests a change in the character of π bonds with the electronic excitation. [ABSTRACT FROM AUTHOR]

We study the accuracy of excited state (ES) geometries using optimally tuned LC-PBE functionals with tuning based on GW quasiparticle energies. We compare the results obtained with the PBE, PBE0, non-tuned, and tuned LC-PBE functionals with available high-level CC reference values as well as experimental data. First, we compare ES geometrical parameters obtained for three different types of systems: molecules composed of a few atoms, 4-(dimethylamino)benzonitrile (DMABN), and conjugated dyes. To this end, we used wave-function results as benchmarks. Next, we evaluate the accuracy of the theoretically simulated spectra as compared to the experimental ones for five large dyes. Our results show that, besides small compact molecules for which tuning LC-PBE does not allow obtaining geometries more accurate than those computed with standard functionals, tuned range-separated functionals are clearly to be favored, not only for ES geometries but also for 0–0 energies, band shapes, and intensities for absorption and emission spectra. In particular, the results indicate that GW-tuned LC-PBE functionals provide improved matching with experimental spectra as compared to conventionally tuned functionals. It is an open question whether TD-DFT with GW-tuned functionals can qualitatively mimic the actual many-body Bethe–Salpeter (BSE/GW) formalism for which analytic ionic gradients remain to be developed. [ABSTRACT FROM AUTHOR]

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]

A time-dependent vibrational electronic coupled-cluster (VECC) approach is proposed to simulate photo-electron/UV-VIS absorption spectra as well as time-dependent properties for non-adiabatic vibronic models, going beyond the Born–Oppenheimer approximation. A detailed derivation of the equations of motion and a motivation for the ansatz are presented. The VECC method employs second-quantized bosonic construction operators and a mixed linear and exponential ansatz to form a compact representation of the time-dependent wave-function. Importantly, the method does not require a basis set, has only a few user-defined inputs, and has a classical (polynomial) scaling with respect to the number of degrees of freedom (of the vibronic model), resulting in a favorable computational cost. In benchmark applications to small models and molecules, the VECC method provides accurate results compared to multi-configurational time-dependent Hartree calculations when predicting short-time dynamical properties (i.e., photo-electron/UV–VIS absorption spectra) for non-adiabatic vibronic models. To illustrate the capabilities, the VECC method is also successfully applied to a large vibronic model for hexahelicene with 14 electronic states and 63 normal modes, developed in the group by Aranda and Santoro [J. Chem. Theory Comput. 17, 1691, (2021)]. [ABSTRACT FROM AUTHOR]

Two new supramolecular photocatalysts made of covalently linked Ru(II) polypyridine chromophore subunits ([Ru(bpy)3]2+-type species; bpy = 2,2′-bipyridine) and [RuL(pic)2] (L = 2,2′-bipyridine-6,6′-dicarboxylic acid; pic = 4-picoline) water oxidation catalyst subunits have been prepared. The new species, 1 and 2, contain chromophore and catalyst subunits in the molecular ratios 1:1 and 1:2, respectively. The model chromophore species [Ru(bpy)2(L1)]2+ (RuP1; L1=4-[2-(4-pyridyl)-2-hydroxyethyl]-4-methyl-2,2′-bipyridine) and [Ru(bpy)2(L2)]2+ (RuP2; L2 = 4,4′-bis[2-(4-pyridyl)-2-hydroxyethyl]-2,2′-bipyridine) have also been prepared. The absorption spectra, oxidation behavior, and luminescent properties of 1 and 2 have been studied, and the results indicate that each subunit largely maintains its own properties in the supramolecular species. However, the luminescence of the chromophore subunits is significantly quenched in 1 and 2 in comparison with the luminescence of the respective model species. Both 1 and 2 exhibit catalytic water oxidation in the presence of cerium ammonium nitrate, exhibiting an I2M mechanism, with a better efficiency than the known catalyst [RuL(pic)2] under the same experimental conditions. Upon light irradiation, in the presence of persulfate as a sacrificial acceptor agent, 1 and 2 are more efficient photocatalysts than a system made of separated [Ru(bpy)3]2+ and [RuL(pic)2] species, highlighting the advantage of using multicomponent, supramolecular species with respect to isolated species. The O–O bond formation step is I2M, even in the photo-driven process. The photocatalytic process of 2 is more efficient than that of 1, with the turnover frequency reaching a value of 1.2 s−1. A possible reason could be an increased local concentration of catalytic subunits in the needed bimolecular assembly required for the I2M mechanism in 2 with respect to 1, a consequence of the presence of two catalytic subunits in each multicomponent species 2. [ABSTRACT FROM AUTHOR]

By employing the numerically accurate multiple Davydov Ansatz (mDA) formalism in combination with the thermo-field dynamics (TFD) representation of quantum mechanics, we systematically explore the influence of three parameters—temperature, photonic-mode detuning, and qubit–phonon coupling—on population dynamics and absorption spectra of the Holstein–Tavis–Cummings (HTC) model. It is found that elevated qubit–phonon couplings and/or temperatures have a similar impact on all dynamic observables: they suppress the amplitudes of Rabi oscillations in photonic populations as well as broaden the peaks and decrease their intensities in the absorption spectra. Our results unequivocally demonstrate that the HTC dynamics is very sensitive to the concerted variation of the three aforementioned parameters, and this finding can be used for fine-tuning polaritonic transport. The developed mDA-TFD methodology can be efficiently applied for modeling, predicting, optimizing, and comprehensively understanding dynamic and spectroscopic responses of actual molecular systems in microcavities. [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]

In this work, charge photogeneration and recombination processes of PM6:IDIC-4F and PM6:IDIC blend films were investigated by the steady-state and time-resolved spectroscopies, as well as the time-dependent density functional theory calculations. The peaks in absorption and photoluminescence (PL) spectra of IDIC and IDIC-4F solutions were assigned by combining the experiment and the simulation of UV–vis absorption and PL spectra. For neat acceptor films, the exciton diffusion length of neat IDIC and IDIC-4F films was estimated as ∼28.9 and ∼19.9 nm, respectively. For PM6-based blend films, we find that the fluorine substitution engineering on the IDIC acceptor material can increase the phase separate size of acceptor material in blend films, resulting in the reduction of dissociation efficiencies of acceptor excitons. In addition, we find that the charge recombination in PM6:IDIC-4F is dominated by bimolecular recombination, in comparison to geminate type carrier recombination in PM6:IDIC blend films. In addition, we find that thermal annealing treatment has a weak influence on carrier recombination but slightly reduces the exciton dissociation efficiency of acceptor in PM6:IDIC blend films, leading to a slightly reduced power conversion efficiency of PM6:IDIC solar cells. These results may shed light on the design of high-performance semiconductor molecules for application in solar cells. [ABSTRACT FROM AUTHOR]

The second order cumulant method offers a promising pathway to predicting optical properties in condensed phase systems. It allows for the computation of linear absorption spectra from excitation energy fluctuations sampled along molecular dynamics (MD) trajectories, fully accounting for vibronic effects, direct solute–solvent interactions, and environmental polarization effects. However, the second order cumulant approximation only guarantees accurate line shapes for energy gap fluctuations obeying Gaussian statistics. A third order correction has recently been derived but often yields unphysical spectra or divergent line shapes for moderately non-Gaussian fluctuations due to the neglect of higher order terms in the cumulant expansion. In this work, we develop a corrected cumulant approach, where the collective effect of neglected higher order contributions is approximately accounted for through a dampening factor applied to the third order cumulant term. We show that this dampening factor can be expressed as a function of the skewness and kurtosis of energy gap fluctuations and can be parameterized from a large set of randomly sampled model Hamiltonians for which exact spectral line shapes are known. This approach is shown to systematically remove unphysical contributions in the form of negative absorbances from cumulant spectra in both model Hamiltonians and condensed phase systems sampled from MD and dramatically improves over the second order cumulant method in describing systems exhibiting Duschinsky mode mixing effects. We successfully apply the approach to the coumarin-153 dye in toluene, obtaining excellent agreement with experiment. [ABSTRACT FROM AUTHOR]

A synchrotron based vacuum ultraviolet absorption spectrum for γ-pyrone has been interpreted in terms of singlet excited electronic states using a variety of coupled cluster, configuration interaction, and density functional calculations. The extremely weak spectral onset at 3.557 eV shows eight vibrational peaks, which following previous analyses, are attributed to a forbidden 1A2 state. A contrasting broad peak with a maximum at 5.381 eV has a relatively high cross-section of 30 Mb; this arises from three overlapping states, where a 1A1 state dominates over progressively weaker 1B2 and 1B1 states. After fitting the second band to a polynomial Gaussian function and plotting the regular residuals over 20 vibrational peaks, we have had limited success in analyzing this fine structure. However, the small separation between these three states clearly shows that their vibrational satellites must overlap. Singlet valence and Rydberg state vibrational profiles were determined by configuration interaction using the CAM-B3LYP density functional. Vibrational analysis using both the Franck–Condon and Herzberg–Teller procedures showed that both procedures contributed to the profiles. Theoretical Rydberg states were evaluated by a highly focused CI procedure. The superposition of the lowest photoelectron spectral band on the vacuum ultraviolet spectrum near 6.4 eV shows that the 3s and 3p Rydberg states based on the 2B2 ionic state are present; those based on the other low-lying ionic state (X2B1) are destroyed by broadening; this is a dramatic extension of the broadening previously witnessed in our studies of halogenobenzenes. [ABSTRACT FROM AUTHOR]

Lithium niobate ( LiNbO 3 , LN) on insulator (LNOI) has emerged as a promising platform for integrated photonics, due to the strong optical confinement and excellent nonlinear optical and electrical characteristics of LN crystal. Focused ion beam (FIB) as a versatile technique has become a typical way to fabricate LNOI microstructures. However, due to the bombardment of Ga + ions during fabrication, the LN lattice is damaged, which would deteriorate the performance of LNOI devices. Thus, the recognition of the damage formed by FIB fabrication is necessary for the control and optimization of the properties of LN microstructures. However, previous studies on this issue have not delved into it from a lattice perspective. Here, we conducted an investigation into the damage inflicted on LN film due to FIB fabrication and the subsequent impact of buffered oxide etching (BOE) treatment on this damage using Raman spectroscopy. Our findings indicate that the interaction between Ga + ions and LN film results in lattice amorphization, as well as a reduction in the ionic bonding and lattice stress within LN. Furthermore, absorption spectra were acquired both before and after BOE treatment, revealing the emergence of additional optical losses attributed to Ga + ions. Notably, these defects responsible for optical losses are predominantly concentrated near the surface of the milled LN film, and BOE treatment proves efficient in their removal. This study contributes to further understanding of the defect structure in LN film after FIB fabrication, as well as repairing the damage and, thus, improving the performance of LN microstructures. [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]

Ultraviolet and vacuum ultraviolet photo-absorption spectra of azido (–N3)-based energetic plasticizer, bis(1,3-diazido-prop-2-yl)-malonate (abbreviated as BDAzPM), in the gas phase is recorded at room temperature and in the photon energy range of 5.5–9.9 eV using a synchrotron radiation source. Complementary computational results obtained using the time-dependent density functional theory document the vertical transition energies and oscillator strengths. Comparison of the simulated spectra with the experimental absorption spectrum of BDAzPM reveals that the early part of the absorption spectrum of BDAzPM is of pure valence excitation character, whereas the later intense part of the absorption spectrum is dominated by mixed Rydberg and valence electronic excitations. [ABSTRACT FROM AUTHOR]

We investigate the optical properties appearing in a nanostructure that is composed of an asymmetric double semiconductor quantum dot (SQD) molecule and a metal nanoparticle (MNP). The profile of the total linear absorption spectrum is proportional to the SQD contribution, while the MNP contribution is important. The profile of the doublet of resonances detected on the total linear absorption spectrum creates a transparency window. The doublet is asymmetric for small SQD-MNP distances and has a narrow peak and a wide peak. The width of the transparency window is increased, either with the enhancement of the rate at which the electron tunneling effect takes place within the double SQD molecule or with the decrease of the distance that separates the SQD molecule from the center of the MNP. The steep slope detected on the linear dispersion spectrum for frequencies laying within the transparency window owes its presence to the tunneling induced transparency and leads to slow light production. The corresponding value of the slow down factor is maximized for low values of the electron tunneling rate as well as for low center-to-center distances between the components of the hybrid nanostructure. [ABSTRACT FROM AUTHOR]

The first-order molecular hyperpolarizability (β) dispersion was measured in seven chalcone-based molecules utilizing the tunable femtosecond hyper-Rayleigh scattering (tHRS) technique. Additionally, a theoretical model based on photophysical parameters was employed to better understand β dispersion. Due to the distinct substitution patterns of the aryl/heteroaryl rings within the chalcone structure, varying profiles of one- and two-photon absorption spectra and β dispersion were observed. The applied model highlighted two important factors contributing to achieving high β values: (i) the presence of red-shifted one-photon and two-photon absorption bands; and (ii) the number of discernible absorption bands. To contextualize these results with other molecular structures, we employed the HRS figure of merit (FOM). Remarkably, it was revealed that chemically engineered small chalcone molecules exhibit a FOM comparable to larger quadrupolar and octupolar ones. This underscores the significance of tHRS scattering measurements and their correlation with absorptive parameters in the design and characterization of nonlinear optical materials. [ABSTRACT FROM AUTHOR]

We propose an effective scheme to sense charged particles by employing two-color second-order sidebands (TSSs) in a hybrid optomechanical system. This is realized in an optomechanical cavity with a double-oscillator structure, where the Coulomb force acting on two charged oscillators participates in nonlinear optomechanical interaction. With the aid of mechanical mode splitting induced by the Coulomb force, we report that the TSS spectrum can be generated and enhanced when the strong absorption in the transmission spectrum allows the TSS generated pathways to be readily accessed. More importantly, after seeking two correlations between the TSS spectra and the charged particles deposited on the oscillator, we design a dual-parameter sensor to measure the mass and the charge of the external particles simultaneously. Through evaluating the influence of the thermomechanical noise on the optomechanical sensing device, the resolution for detecting the mass and the charge of the measured particles can be identified as δ m ≈ 1.7 × 10 − 18 g and δ Q ≈ 1.6 × 10 − 18 C , respectively. [ABSTRACT FROM AUTHOR]

Although useful to extract excitation energies of states of double-excitation character in time-dependent density functional theory that are missing in the adiabatic approximation, the frequency-dependent kernel derived earlier [Maitra et al., J. Chem. Phys. 120, 5932 (2004)] was not designed to yield oscillator strengths. These are required to fully determine linear absorption spectra, and they also impact excited-to-excited-state couplings that appear in dynamics simulations and other quadratic response properties. Here, we derive a modified non-adiabatic kernel that yields both accurate excitation energies and oscillator strengths for these states. We demonstrate its performance on a model two-electron system, the Be atom, and on excited-state transition dipoles in the LiH molecule at stretched bond-lengths, in all cases producing significant improvements over the traditional approximations. [ABSTRACT FROM AUTHOR]

Absolute line strengths of several transitions in the ν1 fundamental band of the hydroxyl radical (OH) have been measured by simultaneous determination of hydrogen peroxide (H2O2) and OH upon laser photolysis of H2O2. Based on the well-known quantum yield for the generation of OH radicals in the 248-nm photolysis of H2O2, the line strength of the OH radicals can be accurately derived by adopting the line strength of the well-characterized transitions of H2O2 and analyzing the difference absorbance time traces of H2O2 and OH obtained upon laser photolysis. Employing a synchronized two-color dual-comb spectrometer, we measured high-resolution time-resolved absorption spectra of H2O2 near 7.9 µm and the OH radical near 2.9 µm, simultaneously, under varied conditions. In addition to the studies of the line strengths of the selected H2O2 and OH transitions, the kinetics of the reaction between OH and H2O2 were investigated. A pressure-independent rate coefficient kOH+H2O2 was determined to be [1.97 (+0.10/−0.15)] × 10−12 cm3 molecule−1 s−1 at 296 K and compared with other experimental results. By carefully analyzing both high-resolution spectra and temporal absorbance profiles of H2O2 and OH, the uncertainty of the obtained OH line strengths can be achieved down to <10% in this work. Moreover, the proposed two-color time-resolved dual-comb spectroscopy provides a new approach for directly determining the line strengths of transient free radicals and holds promise for investigations on their self-reaction kinetics as well as radical–radical reactions. [ABSTRACT FROM AUTHOR]

The dynamics of delocalized excitons in light-harvesting complexes (LHCs) can be investigated using different experimental techniques, and transient absorption (TA) spectroscopy is one of the most valuable methods for this purpose. A careful interpretation of TA spectra is essential for the clarification of excitation energy transfer (EET) processes occurring during light-harvesting. However, even in the simplest LHCs, a physical model is needed to interpret transient spectra as the number of EET processes occurring at the same time is very large to be disentangled from measurements alone. Physical EET models are commonly built by fittings of the microscopic exciton Hamiltonians and exciton-vibrational parameters, an approach that can lead to biases. Here, we present a first-principles strategy to simulate EET and transient absorption spectra in LHCs, combining molecular dynamics and accurate multiscale quantum chemical calculations to obtain an independent estimate of the excitonic structure of the complex. The microscopic parameters thus obtained are then used in EET simulations to obtain the population dynamics and the related spectroscopic signature. We apply this approach to the CP29 minor antenna complex of plants for which we follow the EET dynamics and transient spectra after excitation in the chlorophyll b region. Our calculations reproduce all the main features observed in the transient absorption spectra and provide independent insight on the excited-state dynamics of CP29. The approach presented here lays the groundwork for the accurate simulation of EET and unbiased interpretation of transient spectra in multichromophoric systems. [ABSTRACT FROM AUTHOR]

Computational optimal transport is used to analyze the difference between pairs of continuous molecular spectra. It is demonstrated that transport distances which are derived from this approach may be a more appropriate measure of the difference between two continuous spectra than more familiar measures of distance under many common circumstances. Associated with the transport distances is the transport map which provides a detailed analysis of the difference between two molecular spectra and is a key component of our study of quantitative differences between two continuous spectra. The use of optimal transport for comparing molecular spectra is developed in detail here with a set of model spectra, so that the discussion is self-contained. The difference between the transport distance and more common definitions of distance is elucidated for some well-chosen examples and it is shown where transport distances may be very useful alternatives to standard definitions of distance. The transport distance between a theoretical and experimental electronic absorption spectrum for SO2 is studied and it is shown how the theoretical spectrum can be modified to fit the experimental spectrum better adjusting the theoretical band origin and the resolution of the theoretical spectrum. This analysis includes the calculation of transport maps between the theoretical and experimental spectra suggesting future applications of the methodology. [ABSTRACT FROM AUTHOR]

The electronic and vibrational spectra of the meso-tetrakis(4-sulfonatophenyl)-porphyrins (TSPP) have been studied computationally using the PFD-3B functional with time-dependent density functional theory for the excited states. The calculated UV-vis absorption and emission spectra in aqueous solution are in excellent agreement with the experimental measurements of both H2TSPP−4 (monomer) at high pH and H4TSPP−2 (forming J-aggregate) at low pH. Moreover, our calculations reveal an infrared absorption at 1900 cm−1 in the singlet and triplet excited states that is absent in the ground state, which is chosen as a probe for transient IR absorption spectroscopy to investigate the vibrational dynamics of the excited state. Specifically, the S2 to S1 excited state internal conversion process time, the S1 state vibrational relaxation time, and the lifetime of the S1 excited electronic state are all quantitatively deduced. [ABSTRACT FROM AUTHOR]

Developing dyes with high open-circuit photovoltage (Voc) is a vital strategy to improve the power conversion efficiency (PCE) of co-sensitized solar cells (co-DSSCs). Herein, three organic fluorine-containing dyes [YY-ThP(3F), YY-ThP(2F), and YY-ThP(26F)] are designed and synthesized for investigating the fluorine-induced effect on photophysical and photovoltaic performances. Consequently, this effect can significantly broaden the UV–vis absorption spectra of dyes but fail to improve the light-harvesting capability of DSSCs. Strikingly, YY-ThP(3F), featuring 3-position fluorine substitution to cyanoacrylic acid, yields a relatively high Voc compared to the corresponding fluorine-free dye (YY-ThP). Furthermore, the co-sensitization of YY-ThP+YY-ThP(3F) achieves a remarkably high PCE and long-term stability. This work implies that the combination of judicious molecular engineering and co-sensitization is a promising strategy for highly efficient and stable DSSCs. [ABSTRACT FROM AUTHOR]

We present a theoretical study on the structural and electronic properties of the p-dimethylamino-cinnamaldehyde (DMACA) merocyanine molecule in solvents of different polarities by combining the free energy gradient and the average solvent electrostatic configuration methods via an iterative procedure based on the sequential quantum mechanics/molecular mechanics hybrid methodology. Studying such a system in solution is a crucial step for understanding the solvent effects on its properties, which can have implications in fields such as optoelectronics and biophysics. We found that the DMACA molecule presents different geometries in nonpolar and polar solvents, changing from a polyene-like structure with a pyramidal dimethylamino group (in gas phase or nonpolar solvents) to a cyanine-like structure with a planar dimethylamino group in water due to the stabilizing effect of hydrogen bonds between DMACA and water. The molecular absorption spectrum showed a significant change, increasing solvent polarity with a large shift of the lower energy band, while the other two low lying bands did not shift significantly. The study accurately described the solvatochromic shift of the lowest-energy band and analyzed the structure of the excited states in terms of the one-electron transition density matrix, which showed that the dominant excited state (associated with the first lower energy band) is characterized by a local excitation on the benzene ring with charge transfer character to the carbon conjugated segment. [ABSTRACT FROM AUTHOR]

We calculated the one- (OPA) and two-photon absorption (TPA) spectra of two large water-soluble stilbene derivatives presenting TPA cross sections of about 400 GM. However, the reported experimental TPA spectra present a spectral gap region, and a theoretical study of these promising molecules seems now timely and relevant. These molecules are composed of 200 or more atoms, becoming a challenge to obtain the TPA spectra even using density functional theory at the time-dependent quadratic response formalism. Thus, both OPA and TPA were also calculated using the INDO-S semi-empirical method. We used explicit solvent molecules using the sequential-quantum mechanics/molecular mechanics to include the solvent effects. Our results show that different transitions are participating in the OPA and TPA processes and that exchange–correlation functionals, including larger Hartree–Fock contributions, provide a better description of the OPA spectra; however, the opposite trend is observed on the TPA spectra. Alternatively, INDO-S/CISD, including contributions from single and double excitations, systematically describes both OPA and TPA bands with similar shifts and better reproduces the relative intensities of the two TPA bands compared to the experimental ones. The OPA spectra are characterized by a Highest Occupied Molecular Orbital-Lowest Unoccupied Molecular Orbital (HOMO–LUMO) excitation, while the low-energy TPA band is ascribed to a single transition encompassing the (HOMO-1)–LUMO and HOMO–(LUMO+1) excitations and the high-energy one is a combination of several transitions. Thus, although more studies are required to better assess the capability of the INDO-S/CISD method in describing the TPA spectra of large molecules, our results corroborate that it is a promising alternative. [ABSTRACT FROM AUTHOR]

In the present study, the origin of three energy gaps of lanthanum chromium oxide, one arises due to the charge-transfer gap between O-2p and Cr-3d and two arises from the d–d transitions, is analyzed in detail using the diffuse reflectance spectroscopy technique. The spin allowed transitions, such as 4T1(P)→4A2, 4T1(F)→4A2, and 4T2→4A2, and the spin and parity forbidden 2E →4A2 transitions are depicted using a Tanabe–Sugano (T–S) diagram and an absorption spectrum. The high crystal field strength of 3.27 obtained from the T–S diagram provides high directional emission and makes the system suitable for near infrared lasing applications. Moreover, the investigations into the variation of a charge-transfer gap with temperature will provide insights into the modification of numerous optical properties toward development of optoelectronic devices. Using this temperature-dependent diffuse reflectance spectroscopy studies, we have obtained the important optical parameters, such as Urbach energy (Eu) and Urbach focus. Furthermore, first-principles calculations are carried out in order to validate the experimental findings on LaCrO3. The experimental results are in consonance with the charge-transfer gap obtained from the theoretical calculations. Furthermore, the bandgap variation with temperature is fitted using Varshni's relation, and the Debye temperature is calculated. [ABSTRACT FROM AUTHOR]

A synchrotron-based vacuum ultraviolet absorption spectrum (VUV) of quadricyclane (QC) is reported with energies up to 10.8 eV. Extensive vibrational structure has been extracted from the broad maxima by fitting short energy ranges of the VUV spectrum to high level polynomial functions and processing the regular residuals. Comparison of these data with our recent high-resolution photoelectron spectral of QC showed that this structure must be attributed to Rydberg states (RS). Several of these appear before the valence states at higher energies. Both types of states have been calculated by configuration interaction, including symmetry-adapted cluster studies (SAC-CI) and time dependent density functional theoretical methods (TDDFT). There is a close correlation between the SAC-CI vertical excitation energies (VEE) and both Becke 3-parameter hybrid functional (B3LYP), especially Coulomb-attenuating method-B3LYP determined ones. The VEE for several low-lying s-, p, d-, and f-RS have been determined by SAC-CI and adiabatic excitation energies by TDDFT methods. Searches for equilibrium structures for 11,3A2 and 11B1 states for QC led to rearrangement to a norbornadiene structure. Determination of the experimental 00 band positions, which show extremely low cross-sections, has been assisted by matching features in the spectra with Franck–Condon (FC) fits. Herzberg–Teller (HT) vibrational profiles for the RS are more intense than the FC ones, but only at high energy, and are attributed to up to ten quanta. The vibrational fine structure of the RS calculated by both FC and HT procedures gives an easy route to generating HT profiles for ionic states, which usually require non-standard procedures. [ABSTRACT FROM AUTHOR]

We assess the cavity molecular dynamics method for the calculation of vibrational polariton spectra using liquid water as a specific example. We begin by disputing a recent suggestion that nuclear quantum effects may lead to a broadening of polariton bands, finding instead that they merely result in anharmonic red shifts in the polariton frequencies. We go on to show that our simulated cavity spectra can be reproduced to graphical accuracy with a harmonic model that uses just the cavity-free spectrum and the geometry of the cavity as input. We end by showing that this harmonic model can be combined with the experimental cavity-free spectrum to give results in good agreement with optical cavity measurements. Since the input to our harmonic model is equivalent to the input to the transfer matrix method of applied optics, we conclude that cavity molecular dynamics cannot provide any more insight into the effect of vibrational strong coupling on the absorption spectrum than this transfer matrix method, which is already widely used by experimentalists to corroborate their cavity results. [ABSTRACT FROM AUTHOR]

Non-impact effects in the absorption spectra of HCl in various collision-partners are investigated both experimentally and theoretically. Fourier transform spectra of HCl broadened by CO2, air, and He have been recorded in the 2-0 band region at room temperature and for a wide pressure range, from 1 to up to 11.5 bars. Comparisons between measurements and calculations using Voigt profiles show strong super-Lorentzian absorptions in the troughs between successive lines in the P and R branches for HCl in CO2. A weaker effect is observed for HCl in air, while for HCl in He, Lorentzian wings are in very good agreement with measurements. In addition, the line intensities retrieved by fitting the Voigt profile on the measured spectra decrease with the density of the perturber. This perturber-density dependence decreases with the rotational quantum number. For HCl in CO2, the decrease in the retrieved line intensity can reach 2.5% per amagat for the first rotational quantum numbers. This number is about 0.8% per amagat for HCl in air, while for HCl in He, no density dependence of the retrieved line intensity is observed. Requantized classical molecular dynamics simulations have been performed for HCl–CO2 and HCl–He in order to simulate the absorption spectra for various perturber-density conditions. The density dependence of the intensities retrieved from the simulated spectra and the predicted super-Lorentzian behavior in the troughs between lines are in good agreement with experimental determinations for both HCl–CO2 and HCl–He. Our analysis shows that these effects are due to incomplete or ongoing collisions, which govern the dipole auto-correlation function at very short times. The effects of these ongoing collisions strongly depend on the details of the intermolecular potential: they are negligible for HCl–He but significant for HCl–CO2 for which a line-shape model beyond the impact approximation will be needed to correctly model the absorption spectra from the center to the far wings. [ABSTRACT FROM AUTHOR]

The absorption spectra of congenetic wurtzite (WZ) and zincblende (ZB) CdS magic-sized clusters are investigated. We demonstrate that the exciton peak positions can be tuned by up to 500 meV by varying the strong coupling between X-type ligands and the semiconductor cores, while the addition of L-type ligands primarily affects cluster midgap states. When Z-type ligands are displaced by L-type ligands, red shifts in the absorption spectra are observed, despite the fact there is a small decrease in cluster size. Density functional theory calculations are used to explain these findings and they reveal the importance of Cd and S dangling bonds on the midgap states during the Z- to L-type ligand exchange process. Overall, ZB CdS clusters show higher chemical stability than WZ clusters but their optical properties exhibit greater sensitivity to the solvent. Conversely, WZ CdS clusters are not stable in a Lewis base-rich environment, resulting in various changes in their spectra. Our findings enable researchers to select capping ligands that modulate the optical properties of semiconductor clusters while maintaining precise control over their solvent interactions. [ABSTRACT FROM AUTHOR]

In this paper, we present dyadic adaptive HOPS (DadHOPS), a new method for calculating linear absorption spectra for large molecular aggregates. This method combines the adaptive HOPS (adHOPS) framework, which uses locality to improve computational scaling, with the dyadic HOPS method previously developed to calculate linear and nonlinear spectroscopic signals. To construct a local representation of dyadic HOPS, we introduce an initial state decomposition that reconstructs the linear absorption spectra from a sum over locally excited initial conditions. We demonstrate the sum over initial conditions can be efficiently Monte Carlo sampled and that the corresponding calculations achieve size-invariant [i.e., O (1) ] scaling for sufficiently large aggregates while trivially incorporating static disorder in the Hamiltonian. We present calculations on the photosystem I core complex to explore the behavior of the initial state decomposition in complex molecular aggregates as well as proof-of-concept DadHOPS calculations on an artificial molecular aggregate inspired by perylene bis-imide to demonstrate the size-invariance of the method. [ABSTRACT FROM AUTHOR]

Real-time (RT) electron density propagation with time-dependent density functional theory (TDDFT) or Hartree–Fock (TDHF) is one of the most popular methods to model the charge transfer in molecules and materials. However, both RT-TDHF and RT-TDDFT within the adiabatic approximation are known to produce inaccurate evolution of the electron density away from the ground state in model systems, leading to large errors in charge transfer and erroneous shifting of peaks in absorption spectra. Given the poor performance of these methods with small model systems and the widespread use of the methods with larger molecular and material systems, here we bridge the gap in our understanding of these methods and examine the size-dependence of errors in RT density propagation. We analyze the performance of RT density propagation for systems of increasing size during the application of a continuous resonant field to induce Rabi-like oscillations, during charge-transfer dynamics, and for peak shifting in simulated absorption spectra. We find that the errors in the electron dynamics are indeed size dependent for these phenomena, with the largest system producing the results most aligned with those expected from linear response theory. The results suggest that although the RT-TDHF and RT-TDDFT methods may produce severe errors for model systems, the errors in charge transfer and resonantly driven electron dynamics may be much less significant for more realistic, large-scale molecules and materials. [ABSTRACT FROM AUTHOR]

Theoretical description of electronically excited states of molecular aggregates at an ab initio level is computationally demanding. To reduce the computational cost, we propose a model Hamiltonian approach that approximates the electronically excited state wavefunction of the molecular aggregate. We benchmark our approach on a thiophene hexamer, as well as calculate the absorption spectra of several crystalline non-fullerene acceptors, including Y6 and ITIC, which are known for their high power conversion efficiency in organic solar cells. The method qualitatively predicts the experimentally measured spectral shape, which can be further linked to the molecular arrangement in the unit cell. [ABSTRACT FROM AUTHOR]

We observed a unique interpillar gap-related surface-enhanced Raman scattering (SERS) behavior of p -aminothiophenol (PATP) molecules from periodic TiO2 nanopillar arrays with three gap sizes of 191, 297 and 401 nm, which is completely different from that on Ag and Ni nanopillar arrays. Especially, the gap-size-dependent charge-transfer (CT) resonance enhancement from TiO2/Ni has been indicated through comparisons of variation trend of SERS intensities with inter-pillar gap size between TiO2/Ni and Ag/TiO2/Ni as well as Ni nanoarrays, and been confirmed by spectra of ultraviolet–visible absorption and photoluminescence. Results demonstrate that the CT resonance enhancement is more susceptible to the change of the gap size compared with the surface plasmon resonance (SPR) enhancement in TiO2/Ni nanoarrays. Hence, SPR and CT enhancement showing different variation trend and rate with the gap size that leads to a different relative contribution of CT resonance to the overall SERS enhancement as gap size changes, and consequently results in a unique gap-related SERS behavior for TiO2/Ni nanoarrays. The present study is not only helpful for investigating SERS mechanism for semiconductors but also providing a method to design and optimize periodic metal/semiconductor SERS substrates in a controllable way. [ABSTRACT FROM AUTHOR]

We present the two‐photon absorption (2PA) spectrum of aqueous thiocyanate calculated using high‐level quantum‐chemistry methods. The 2PA spectrum is compared to the one‐photon absorption (1PA) spectrum computed using the same computational protocol. Although the two spectra probe the same set of electronic states, the intensity patterns are different, leading to an apparent red‐shift of the 2PA spectrum relative to the 1PA spectrum. The presented analysis explains the intensity patterns and attributes the differences between the 1PA and 2PA spectra to the native symmetry of isolated SCN −, which influences the spectra in the low‐symmetry solvated environment. The native symmetry also manifests itself in variations of the polarization ratio (e.g., parallel vs. perpendicular cross sections) across the spectrum. The presented results highlight the potential of 2PA spectroscopy and high‐level quantum‐chemistry methods in studies of condensed‐phase phenomena. [ABSTRACT FROM AUTHOR]

The enhancement of photo-Fenton performance in BiOBr via a synergistic approach of efficient adsorption and reduced recombination of photogenerated carriers is an innovative strategy. This research employs an in-situ precipitation process to incorporate modified TiO₂ onto the surface of BiOBr, while integrating polyethylene glycol to create an S-type heterojunction material (FT-OVs/PEG-BiOBr). The incorporation of hydroxyl groups by PEG facilitates π-π conjugation and hydrogen bonding, thereby enhancing the adsorption capacity of FT-OVs/PEG-BiOBr. The presence of oxygen vacancies extends the absorption spectrum into the infrared region, and the electron trap mechanism substantially decreases the recombination of photogenerated carriers. The developed S-type heterojunction structure efficiently directs electron transport along a specific pathway. Photoluminescence (PL) studies reveal a further reduction in the recombination of photogenerated carriers. Remarkably, there is a significant synergistic effect between adsorption and low recombination of photogenerated carriers. A profound photo-Fenton synergistic effect is observed at pH 3, leading to degradation rates of RhB and TCH of approximately 98% and 85%, respectively, within 10 min. The degradation pathway of RhB has been investigated using LC-MS analysis, and 1O₂ has been identified as the primary active species through ESR testing. This study presents a novel structural approach to significantly enhance the efficiency of catalysts in Fenton systems. [ABSTRACT FROM AUTHOR]

This study employs first-principles calculation to investigate the MoSi 2 N 4 /SiC heterojunction. It aims to determine the structure, electronic, and optical properties of the heterojunction and assess the impact of varying vertical electric fields and biaxial strains on these properties. The results show that the MoSi 2 N 4 /SiC heterojunction is a direct bandgap semiconductor, exhibiting a band gap of 0.31 eV. This heterojunction benefits from a built-in electric field originating from the SiC layer and extending to the MoSi 2 N 4 layer. The optical absorption peaks in the ultraviolet region are significantly more intense than those in MoSi 2 N 4 and SiC monolayers, particularly at a wavelength of 172 nm, where the intensity reaches 1.99 × 106 cm−1. The study also shows that an increasing positive vertical electric field leads to a rising band gap. On the other hand, increasing tensile or compressive strain causes a gradual decline in the band gap. Specifically, at a strain of −8 %, the absorption peak intensity reaches 3.4 × 106 cm−1 at 172 nm, and the absorption spectrum broadens to 722 nm at an 8 % strain. In conclusion, the MoSi 2 N 4 /SiC heterojunction shows promise for enhancing the optical properties of two-dimensional materials and offers valuable insights for the development of efficient new ultraviolet devices. [ABSTRACT FROM AUTHOR]

Single crystals of garnets with composition Yb 2.96- x Y x Ho 0.04 Al 5 O 12 (x = 0, 2.92, 2.96) were grown by optical floating zone method, and shown by XRD measurements to be in the cubic phase. EDS spectra show that Ho3+ and Yb3+ were homogenously distributed in the structure. As shown by the transmission and absorption spectra, the Yb 2.96-x Y x Ho 0.04 Al 5 O 12 crystals are highly transparent and can function as excellent optical crystals. Compared to the Y 2.96 Ho 0.04 Al 5 O 12 crystal, the Yb 2.96 Ho 0.04 Al 5 O 12 crystal has an additional strong broad absorption in the 836–1070 nm range, which increases its absorption of 980 nm photons. The optical band gaps of the Yb 2.96- x Y x Ho 0.04 Al 5 O 12 crystals decrease with increasing Yb 2 O 3 concentration. Furthermore, differences with Yb 2 O 3 concentrations in the Yb 2.96- x Y x Ho 0.04 Al 5 O 12 crystals were observed for the first time in the up- and down-conversion photoluminescence. Under excitation with a 980 nm laser, the up-conversion PL spectra of the Yb 2.96- x Y x Ho 0.04 Al 5 O 12 crystals show several emission peaks at 548 nm, 665 nm and 775 nm, and their intensities increase with Yb 2 O 3 concentrations. In the Yb 2.96 Ho 0.04 Al 5 O 12 crystal, Yb3+ not only is a component of the garnet structure, but it also acts as a sensitizer. In regards of down-conversion, under excitation at 454 nm, the down-conversion PL spectra of the Yb 2.96- x Y x Ho 0.04 Al 5 O 12 crystals show strong emission peaks at 550 nm, and their intensities decrease with increasing Yb 2 O 3 concentrations, which is considered to be the consequence of increasing matrix density. [ABSTRACT FROM AUTHOR]

Restricted light absorption spectra in conjunction with intrinsic material instability present formidable challenges to the effective functionality of existing photocatalytic systems. As a viable alternative to conventional photocatalytic materials, hydrogen-bonded organic frameworks (HOFs) can form conjugated systems through coupling and stacking effects, which can effectively promote the rapid transfer of charge over a wide optical range and improve the stability and photocatalytic activity. Herein we employ a large conjugate system material based on cobalt phthalocyanine (HOF-CoPcTc) as a proof of concept for this approach. The carboxyl groups in the tetracarboxy cobalt phthalocyanine were conjugated with phthalocyanine macrocycles which could extend the π-electron conjugation system of HOF-CoPcTc. Remarkably, the decomposition rate of the sulfamethoxazole (SMX) molecule in an aqueous solution was about 99% after 120 min under visible light irradiation for HOF-CoPcTc, which is a significant 9.78-fold improvement over that of the ligand CoPcTc. This study demonstrated that metal phthalocyanine compositions with carboxyl groups can be used to successfully synthesize HOF materials for large conjugated systems and provide a useful method for achieving efficient photocatalytic degradation of antibiotics. [ABSTRACT FROM AUTHOR]

The spin‐orbit coupling corrected absorption spectra of osmium complexes, [Os(bpy)3$$ {}_3 $$]2+$$ {}^{2+} $$ and [Os(phen)3$$ {}_3 $$]2+$$ {}^{2+} $$, were calculated by using ab initio multireference perturbation method (NEVPT2) with relativistic effects taken into account throughout ZORA approximation and corresponding all‐electron basis sets. For the same purpose, the time‐dependent DFT techniques were used. A very good agreement between NEVPT2 and experimental spectra should be highlighted, especially for the MLCT transitions that occur in visible and near‐UV regions (16,000−33,000$$ 16,000-33,000 $$ cm−1$$ {}^{-1} $$). Moreover, the present study offers description of excited states of titled osmium complexes and their spectra interpretation using molecular orbitals. [ABSTRACT FROM AUTHOR]

By constructing a Ag2O/Bi4O5I2 p–n heterojunction and applying a heat-localization microreactor, efficient photocatalysis enhanced by both photoinduced carrier separation and the photothermal effect was realized. This work focuses on the utilization of near-infrared light to broaden the absorption spectrum and accelerate the transportation of carriers. Through the production and localization of heat, it provides a novel thought for full-spectrum photocatalysis. [ABSTRACT FROM AUTHOR]

Polylactic acid (PLA) has attracted increasing interest as a sustainable plastic because it can be degraded into CO2 and H2O in nature. However, this process is sluggish, and even worse, it is a CO2‐emitting and carbon resource waste process. Therefore, it is highly urgent to develop a novel strategy for recycling post‐consumer PLA to achieve a circular plastic economy. Herein, we report a one‐pot photoreforming route for the efficient and selective amination of PLA waste into value‐added alanine using CoP/CdS catalysts under mild conditions. Results show the alanine production rate can reach up to 2.4 mmol gcat−1 h−1, with a high selectivity (>75 %) and excellent stability. Time‐resolved transient absorption spectra (TAS) reveal that CoP can rapidly extract photogenerated electrons from CdS to accelerate proton reduction, favoring hole‐dominated PLA oxidation to coproduce alanine. This study offers an appealing way for upcycling PLA waste and creates new opportunities for green synthesis of amino acids. [ABSTRACT FROM AUTHOR]

The influence of ionizing irradiation on the thermochromic properties of [NH2(C2H5)2]2CuCl4 (DEACC) microcrystals incorporated into a polystyrene matrix was investigated. This composite was found to possess thermochromic properties very similar to those in a bulk crystal although its thermochromic phase transition was shifted toward higher temperatures due to the tensions arising within the interface between the polystyrene matrix and the microcrystal. The similar doses of ionizing radiation cause much more pronounced changes in the thermochromic properties of the microcrystals in comparison with a bulk crystal. The main impact consists in the considerable shift of the phase transition temperature derived from the D(T) hysteresis loops toward lower values that were explained by the breaking of the chemical bonds between the polymer matrix and the microcrystals and the corresponding diminishing of the surface strains. The transformation of the discontinuous phase transition into the continuous one under the influence of irradiation was also discussed. [ABSTRACT FROM AUTHOR]

We calculate the two-phonon contribution to the dielectric susceptibility of diamond at room and elevated temperatures, utilizing a general a b initio model that can be extended to higher n phonon processes. We calculate the second-order dipole moments using a finite displacement method to calculate the derivatives of the Born effective charge tensor. Specifically, we use results obtained from density-functional theory and density-functional perturbation theory in this finite displacement method to calculate the dipole moments of diamond in the two-phonon case. We use the calculated dipole moment to determine the contribution of two-phonon processes to the dielectric susceptibility. We then calculate the absorption curve as a function of wave-number at room or elevated temperatures. Our results indicate that the calculated absorption is in good agreement with previous calculations, and that it increases in magnitude with temperature while maintaining a consistent shape. [ABSTRACT FROM AUTHOR]

Organic solar cells (OSCs) are still suffering from the low light utilization and unstable under ultraviolet irradiation. To tackle these challenges, we design and synthesize a non‐fused acceptor based on 1‐(2‐butyloctyl)‐1H‐pyrrole as π‐bridge unit, denoted as GS70, which serves as active layer in the front‐cell for constructing tandem OSCs with a parallel configuration. Benefiting from the well‐complementary absorption spectra with the rear‐cell, GS70‐based parallel tandem OSCs exhibit an improved photoelectron response over the range between 600–700 nm, yielding a high short‐circuit current density of 28.4 mA cm−2. The improvement in light utilization translates to a power conversion efficiency of 19.4 %, the highest value among all parallel tandem OSCs. Notably, owing to the intrinsic stability of GS70, the manufactured parallel tandem OSCs retain 84.9 % of their initial PCE after continuous illumination for 1000 hours. Overall, this work offers novel insight into the molecular design of low‐cost and stability non‐fused acceptors, emphasizing the importance of adopting a parallel tandem configuration for achieving efficient light harvesting and improved photostability in OSCs. [ABSTRACT FROM AUTHOR]

Density functional study (DFT) is performed for understanding the reactivity, aromaticity, and UV-visible absorption spectra of chrysene-based materials. Effect of BN doping on the said parameters are analyzed along with the effect of –Me (methyl), –OH (hydroxyl), –CHO (formyl) –COOH (carboxyl) and –CN (cyano) substituents. Global reactivity parameters viz. energy of HOMO (E HOMO), global hardness (η), chemical potential (μ) and electrophilicity (ω) are computed. Nucleus independent chemical shifts (NICS) values are estimated to study the variation in aromaticity. Time dependent density functional theory (TD-DFT) is used to study the UV–Visible absorption spectra. Effects of BN doping and substituents on corresponding dipole moments and band gaps are also analyzed. Presence of BN unit and/or substituents induced considerable impact on global reactivity, dipole moment, band gap and aromaticity of the chosen systems, especially for BN doped chrysene at the edge. Absorption spectra which are red shifted in presence of BN and substituents are mostly found within the UV-region. [ABSTRACT FROM AUTHOR]

Controlled synthesis of lead‐halide perovskite crystals is challenging yet attractive because of the pivotal role played by the crystal structure and growth conditions in regulating their properties. This study introduces data‐driven strategies for the controlled synthesis of oriented quasi‐spherical CsPbBr3, alongside an investigation into the synthesis mechanism. High‐throughput rapid characterization of absorption spectra and color under ultraviolet illumination was conducted using 23 possible ligands for the synthesis of CsPbBr3 crystals. The links between the absorption spectra slope (difference in the absorbance at 400 nm and 450 nm divided by a wavelength interval of 50 nm) and crystal size were determined through statistical analysis of more than 100 related publications. Big data analysis and machine learning were employed to investigate a total of 688 absorption spectra and 652 color values, revealing correlations between synthesis parameters and properties. Ex situ characterization confirmed successful synthesis of oriented quasi‐spherical CsPbBr3 perovskites using polyvinylpyrrolidone and Acacia. Density functional theory calculations highlighted strong adsorption of Acacia on the (110) facet of CsPbBr3. Optical properties of the oriented quasi‐spherical perovskites prepared with these data‐driven strategies were significantly improved. This study demonstrates that data‐driven controlled synthesis facilitates morphology‐controlled perovskites with excellent optical properties. [ABSTRACT FROM AUTHOR]

Absorption spectra of red blood cell (RBC) suspensions are investigated in an osmolarity range in the medium from 200 mOsm to 900 mOsm. Three spectral parameters are used to characterize the process of swelling or shrinkage of RBC—the absorbance at 700 nm, the Soret peak height relative to the spectrum background, and the Soret peak wavelength. We show that with an increase in the osmolarity, the absorbance at 700 nm increases and the Soret peak relative height decreases. These changes are related to the changes in the RBC volume and the resulting increase in the hemoglobin intracellular concentration and index of refraction. Confocal microscopy and flow cytometry measurements supported these conclusions. The maximum wavelength of the Soret peak increases with increasing osmolarity due to changes in the oxygenation state of hemoglobin. Using these spectrum parameters, the process of osmosis in RBCs can be followed in real time, but it can also be applied to various processes, leading to changes in the volume and shape of RBCs. Therefore, we conclude that UV–Vis absorption spectrophotometry offers a convenient, easily accessible, and cost-effective method to monitor changes in RBC, which can find applications in the field of drug discovery and diagnostics of RBC and hemoglobin disorders. [ABSTRACT FROM AUTHOR]