Transition Moment Research Articles

Determining Excited-State Absorption Properties of a Quinoid Flavin by Polarization-Resolved Transient Spectroscopy.

As important naturally occurring chromophores, photophysical/chemical properties of quinoid flavins have been extensively studied both experimentally and theoretically. However, little is known about the transition dipole moment (TDM) orientation of excited-state absorption transitions of these important compounds. This aspect is of high interest in the fields of photocatalysis and quantum control studies. In this work, we employ polarization-associated spectra (PAS) to study the excited-state absorption transitions and the underlying TDM directions of a standard quinoid flavin compound. As compared to transient absorption anisotropy (TAA), an analysis based on PAS not only avoids diverging signals but also retrieves the relative angle for ESA transitions with respect to known TDM directions. Quantum chemical calculations of excited-state properties lead to good agreement with TA signals measured in magic angle configuration. Only when comparing experiment and theory for TAA spectra and PAS, do we find deviations when and only when the S0 → S1 of flavin is used as a reference. We attribute this to the vibronic coupling of this transition to a dark state. This effect is only observed in the employed polarization-controlled spectroscopy and would have gone unnoticed in conventional TA.

Longitudinal Extension of Double π-Helix Enables Near-Infrared Amplified Dissymmetry and Chiroptical Response.

Near-infrared (NIR) circularly polarized light absorbing or emitting holds great promise for highly sensitive and precise bioimaging, biosensing, and photodetectors. Aiming at designing NIR chiral molecular systems with amplified dissymmetry and robust chiroptical response, herein, we present a series of double π-helical dimers with longitudinally extended π-entwined substructures via Ullmann or Yamamoto homocoupling reactions. Circular dichroism (CD) spectra revealed an approximate linear bathochromic shift with the rising number of naphthalene subunits, indicating a red to NIR chiroptical response. Particularly, the terrylene diimide-entwined dimers exhibited the strongest CD intensities, with the maximal |Δε| reaching up to 393 M-1 cm-1 at 666 nm for th-TDI[2]; and a record-high chiroptical response (|ΔΔε|) between the neutral and dianionic species of 520 M-1 cm-1 at 833 nm for th-TDI[2]Cl was achieved upon further reduction to its dianionic state. Time-dependent density functional theory (TDDFT) calculations suggested that the pronounced intensification of the CD spectra originated from a simultaneous enhancement of both electric (μ) and magnetic (m) transition dipole moments, ultimately leading to an overall increase in the rotatory strength (R). Notably, the circularly polarized luminescence (CPL) brightness (BCPL) reached 77 M-1 cm-1 for th-TDI[2]Cl, among the highest values reported for NIR-CPL emitters. Furthermore, all chiral dianions exhibited excellent air stability under ambient conditions with half-life times of up to 10 days in N-methylpyrrolidone (NMP), which is significant for future biological applications and chiroptic switches.

Synthesis, characterization and color-purity near-infrared (NIR; λem = 780 nm) phosphorescence of one C1-symmetric [Ir(C^N)2(N^O)]-bis-heteroleptic Ir(III)-complex

In sharp contrast to the success of Ir(III)-complex-based visible-phosphors, the molecular design of their efficient NIR-emissive counter-parts, as constrained by the so-called “energy gap law”, is distinctively difficult. Especially, it remains a great challenge to develop new Ir(III)-complex-based phosphors with both efficient and color-purity NIR-emission. Herein, based on the molecular design of [Ir(dpbq)2(L)], the highly conjugated HC^N-main ligand Hdpbq renders the desirable color-purity NIR-phosphorescence (λPL = 780 nm), and the electron-rich while N^OH-ancillary HL is beneficial to augmented 3MLCT effect and large transition dipole moment (TDM). Accordingly, its color-purity NIR-phosphorescent efficiency (ΦPL = 3.9 %) is significantly higher than those (ΦPL = 1.9–2.5 %) of the [Ir(dpbq)2(O^O)]-analogue.

Optical magnetic field enhancement using ultrafast azimuthally polarized laser beams and tailored metallic nanoantennas

Structured light provides unique opportunities to spatially tailor the electromagnetic field of laser beams. These include the possibility of a sub-wavelength spatial separation of their electric and magnetic fields, which would allow isolating interactions of matter with pure magnetic (or electric) fields. This could be particularly interesting in molecular spectroscopy, as excitations due to electric and—usually very weak—magnetic transition dipole moments can be disentangled. In this work, we show that the use of tailored metallic nanoantennas drastically enhances the strength of the longitudinal magnetic field carried by an ultrafast azimuthally polarized beam (by a factor of ∼65), which is spatially separated from the electric field by the beam’s symmetry. Such enhancement is due to favorable phase-matching of the magnetic field induced by the electric current loops created in the antennas. Our particle-in-cell simulation results demonstrate that the interactions of moderately intense (∼1011  W/cm2) and ultrafast azimuthally polarized laser beams with conical, parabolic, Gaussian, or logarithmic metallic nanoantennas provide spatially isolated magnetic field pulses of several tens of Tesla.

Controlling Chirogenic Effects in Porphyrin Based Supramolecular Systems: Theoretical Analysis Versus Experimental Observations.

Electronic circular dichroism (ECD) spectroscopy is a widely employed method for studying chiral analysis, requiring the presence of a chromophore close to a chiral centre. Porphyrinoids are found to be one of the best chromophoric systems serving for this purpose and enabling the application of ECD spectroscopy for chirality determination across diverse classes of organic compounds. Consequently, it is crucial to understand the induction mechanisms of ECD in the porphyrin-based complexes. The present study explores systematically the influence of secondary chromophores, bonded to an achiral zinc porphyrin or to chiral guest molecules, on the B-region of ECD spectra using the time-dependent density functional theory (TD-DFT) calculations. The study analyses the impact of change in both the conformation of achiral porphyrin (host) and change in position and conformation of chiral organic molecule (guest) on the B-band of ECD spectra (energy, intensity, sign of Cotton effect). Finally, conclusions made on model complexes are applied to published experimental data, contributing to a deeper understanding of various factors influencing ECD spectra in chiral systems. In addition, a computer program aimed to help rationalise ECD spectra by visualizing corresponding orbital energies, rotatory strengths, electric and magnetic transition moments, and angles between them, is presented.

Modeling the performance and bandwidth of single-atom adiabatic quantum memories

Quantum memories are essential for quantum repeaters, which will form the backbone of the future quantum internet. Such memory can capture a signal state for a controllable amount of time, after which this state can be retrieved. In this work, we theoretically investigated how atomic material and engineering parameters affect the performance and bandwidth of a quantum memory. We have applied a theoretical model for quantum memory operation based on the Lindblad master equation and adiabatic quantum state manipulation. The materials’ properties and their uncertainty are evaluated to determine the performance of Raman-type quantum memories by showcasing two defects in two-dimensional hexagonal boron nitride. We have derived a scheme to calculate the signal bandwidth based on the material parameters as well as the maximum efficiency that can be realized. The bandwidth depends on four factors: the signal photon frequency, the dipole transition moments in the electronic structure, the cavity volume, and the strength of the external control electric field. As our scheme is general and independent of materials, it can be applied to many other quantum materials with a suitable three-level structure. We, therefore, provided a promising route for designing and selecting materials for quantum memories. Our work is, therefore, an important step toward the realization of a large-scale quantum network.

Shape-Dependent Optical Waveguides and Low-Threshold Lasers from Polymorphic Two-Dimensional Organic Single Crystals.

Organic single crystals (OSCs) with uniform morphologies and highly ordered molecular aggregations are promising for high-performance optoelectronic devices, such as organic solid-state lasers (OSSLs), organic light-emitting transistors (OLETs), and organic light-emitting diodes (OLEDs). However, manipulating OSC morphologies and aggregation is challenging. In this study, we synthesized two-dimensional (2D) OSCs of 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) in hexagonal and parallelogram microplate (H-MP and P-MP) forms. Both types exhibit H-aggregation in the 2D plate plane but with different molecular transition dipole moment (TDM) orientations. This leads to different photon coupling modes with H-MP and P-MP microcavities. H-MPs enable isotropic 2D-waveguiding, forming whispering gallery mode (WGM) resonators, while P-MPs create unidirectional waveguiding, forming Fabry-Pérot mode (FP) resonators. These resonators can generate low-threshold laser emissions at 467 and 473 nm, respectively, and exhibit superior lasing stability with a half-life exceeding 2 h. Our BSBCz microplate OSCs are attractive candidates to combine controlled organic microcavities with photon transporting for realizing future integrated optoelectronic devices.

Quantum calculation of the pressure broadening of H and K lines of Ca+ calcium ion in a gaz of ground-state He helium atoms

In this theoretical study, we have conducted calculations to investigate the pressure broadening of the H ( 4 s 2 S 1 / 2 − 4 p 2 P 1 / 2 ) and the K ( 4 s 2 S 1 / 2 − 4 p 2 P 3 / 2 ) lines of the Ca + calcium ion in a gas of ground-state He helium atoms. The focus of our work is to determine the profiles of the pressure-broadened resonance lines and analyse their behaviour under the influence of binary collisions between Ca + ions and He atoms. To achieve this, we constructed accurate potential energy curves for the ground X 2 Σ 1 / 2 + and the excited D 2 Π 1 / 2 , D 2 Π 3 / 2 and E 2 Σ 1 / 2 + states. Additionally, we constructed the corresponding transition dipole moments based on the data obtained through high-level ab initio methods, including SA-CASSCF, MRCI, and SO coupling, with Davidson and BSSE corrections. The study spans a range of temperatures from 4000 K to 12,000 K and wavelengths from 200 nm to 500 nm . The theoretical profile is characterised by dominant free-free transitions. In the vicinity of the 436 nm wavelength position, there is a satellite peak in the red wing, attributed to the contribution of D 2 Π 1 / 2 ⟵ X 2 Σ 1 / 2 + and D 2 Π 3 / 2 ⟵ X 2 Σ 1 / 2 + transitions. Our findings are in good agreement with previous theoretical results.

Multireference Correlated Oscillator Strengths from Adiabatic Connection Approaches Based on Extended Random Phase Approximation.

We show that accurate oscillator strengths can be obtained from adiabatic connection (AC) approaches based on the extended random phase approximation (ERPA) combined with multireference (complete active space, CAS) wave functions. The oscillator strengths calculated using the perturbation-corrected ERPA transition density matrices, proposed in this work, and the excitation energies calculated with recently introduced AC correlation energy methods, AC0 and AC0D, compete with accuracy in the perturbational CASPT2 approach and require less computational effort. AC0 and AC0D methods scale more favorably with the number of active orbitals than multiconfigurational perturbation approaches like CASPT2 and NEVPT2 thanks to their dependence on reduced density matrices up to the order of 2. Importantly, the newly developed approach for computing correlated transition dipole moments does not entail any additional costs, as all intermediate quantities become available when AC0 energies are being computed. We also test the performance of the recently proposed AC method corrected for the negative-transition contributions to the correlation energy, AC0D, for triplet excitation energies. Similarly, as for the singlet excitations, the correction improves the performance of the AC0 method, particularly for the low-lying excited states.

Generalized Transition Moment and Oscillator Strength for Optimal Control of Excited States Using Near-Field Light.

The near field is a highly localized light field that is present in the vicinity of materials. It holds considerable potential for manipulating molecular excitation through the design of nanostructures. To that end, a simple yet applicable computational method is required. This letter presents an optimization strategy to achieve targeted electronic excitation in molecules using near-field light. The generalized transition moment and oscillator strength based on the multipolar Hamiltonian can incorporate key parameters affecting the near field, including shape, size, and material composition. This calculation helps optimize electronic transitions through manipulation of the aforementioned parameters. The feasibility of the proposed scheme was demonstrated using a scanning tunneling microscopic setup with light, wherein the near field is controlled by varying the tip position in two dimensions. This approach paves the way for further innovations, which may ultimately enable precise control of molecular behavior by using tailored near-field interactions.

Theoretical Insights into the Photophysical Properties of 4CzIPN Doped in Different Hosts: A Multiscale Study.

As a typical thermally activated delayed fluorescence (TADF) emitter with green emission, 4CzIPN has attracted much attention recently. Most studies indicated that 4CzIPN doped in different hosts presented different performances; thus, the hosts should have an obvious influence on its photophysical properties. Herein, the influence of four kinds of hosts, including m-CzPym, m-CzTrz, p-CzPym, and p-CzTrz, on the photophysical properties of 4CzIPN is investigated. Molecular dynamics simulations were performed to simulate the host-guest conformations, and the photophysical properties were studied using the combined quantum mechanics/molecular mechanics method coupled with the thermal-vibration correlation function method. It is found that 4CzIPN in doped films has larger transition dipole moments and spin-orbital coupling constants compared to that in nondoped films. Faster radiative decay, intersystem crossing rates, and higher fluorescence efficiency could be obtained in doped films. Our work helps to better understand the photophysical properties of 4CzIPN in doped films and may favor the design of new hosts.

Study of the different sleep disturbances during the prodromal phase of depression and mania in bipolar disorders.

One of the challenges in bipolar disorder (BD) lies in early detection of the illness and its recurrences, to improve prognosis. Sleep disturbances (SD) have been proposed as reliable predictive markers of conversion. While preliminary studies have explored the relationship between SD and the onset of mood episodes, the results remain heterogeneous and a few have specifically examined patients' perception of prodromal symptoms and their progression until the episode occurs. Identifying prodromes represents a crucial clinical challenge, as it enables early intervention, thereby reducing the severity of BD. Therefore, the objective of this study is to better characterize and evaluate the progressive nature of SD as prodromal symptoms of mood episodes, and patients' perception of it. Patients diagnosed with BD, either hospitalized or seeking treatment for a (hypo)manic or depressive episode benefited from standardized questionnaires, structured interviews, and self-report questionnaires to evaluate SD prior to the current episode, as well as sociodemographic and clinical information. Out of the 41 patients included, 59% spontaneously reported SD prior to the episode, appearing 90 days before depression and 35 days before mania (pre-indexed/spontaneous reports: 51.22% insomnia complaints, 4.88% hypersomnolence complaints, 7.32% parasomnias, 2.44% sleep movements). After inquiry about specific SD, the percentage of patients reporting prodromal SD increased significantly to 83%, appearing 210 days before depression and 112.5 days before mania (post-indexed reports: 75.61% presented with insomnia complaints appearing 150 days before depression and 20 days before mania, 46.34% had hypersomnolence complaints appearing 60 days before depression, 43.9% had parasomnias appearing 210 days before depression and 22.5 days before mania, 36.59% had sleep movements appearing 120 days before depression and 150 days before mania). Of note, bruxism appeared in 35% of patients before mania, and restless legs syndrome in 20% of patients before depression. This study highlights the very high prevalence of SD prior to a mood episode in patients with BD with differences between depressive and manic episodes. The more systematic screening of sleep alterations of the prodromal phase improved the recognition and characterization of different symptoms onset by patients. This underscores the need for precise questioning regarding sleep patterns in patients, to better identify the moment of transition toward a mood episode, referred to as "Chronos syndrome". The study emphasizes the importance of educating patients about the disorder and its sleep prodromal symptoms to facilitate early intervention and prevent recurrences.

SLIMP 2.0: A new version of strong laser interaction model package for atoms and molecules, now with molecular orbital tomography based on high-order harmonic spectra

A new version of strong laser interaction model package for atoms and molecules is presented. Its capacities are enhanced by incorporating modules related to molecular orbital tomography (MOT) in length and velocity forms based on high-order harmonic spectra (HHS). This advanced package enables two-dimensional and three-dimensional MOT of both symmetric and asymmetric molecules using HHS, providing an efficient means for both experimental and theoretical investigations of molecular orbital structures. In addition, it can calculate the precise theoretical orbitals corresponding to those reconstructed by MOT. Furthermore, the package can calculate the transition dipole moment (TDM) in the plane wave approximation and allow for reference MOT based on TDM. It can evaluate the quality of reconstructed orbitals based on HHS and reveal the physical and numerical effects on MOT. This package is suitable for MOT under conditions of driving laser at different intensities and wavelengths, and can be applied to different molecules with various structures. It is designed to facilitate easy expansion for additional capabilities. Program summaryProgram Title: SLIMP, version 2.0CPC Library link to program files:https://doi.org/10.17632/jgcb7m7wwv.1Licensing provisions: GPLv3Programming language: Fortran 90Journal reference of previous version: Comput. Phys. Commun. 192 (2015) 330-341.Does the new version supersede the previous version?: Yes.Reasons for the new version: Molecular orbital tomography (MOT) [1] based on high-order harmonic spectra (HHS) [2] is an important research topic in the field of strong-field physics. It provides an efficient way to probe molecular orbital structures experimentally, which was not considered in the former version of SLIMP [3] and is now included in SLIMP 2.0. The new version package allows performing two-dimensional (2D) and three-dimensional (3D) MOT [4] based on HHS obtained from experiments or simulations, providing reliable detections for many orbitals of interest, either symmetric or asymmetric molecules.Summary of revisions: Extending capacities focus on enabling performing 2D and 3D MOT on symmetric and asymmetric molecules based on HHS, and together the relevantly precise theoretical orbital output, calculation of transition dipole moment (TDM) and reference MOT based on TDM. For 2D MOT, MOT in both length and velocity forms are implemented.Nature of problem: To perform MOT based on HHS, the user needs general reconstruction programs, taking symmetric and asymmetric molecules, 2D and 3D orbitals, and MOT in length and velocity forms into account. In addition, evaluation of imaging quality is required, which can reveal the physical and numerical effects on reconstructions.Solution method: The 2D symmetric and asymmetric, length- and velocity-form, and 3D reconstruction algorithms are implemented based on Fortran 90. Furthermore, this package provides a reference MOT based on directly calculated TDM, served as a comparable result to the reconstructed orbital based on HHS. The comparison between reconstructions based on HHS and TDM can reveal the effects on MOT in physical and numerical aspects.Additional comments including restrictions and unusual features: This package does not include MOT of asymmetric molecules in velocity form. For the 2D MOT based on HHS, the reconstructed 2D projection of gerade, ungerade orbital or the gerade and ungerade components of asymmetric orbital must have the axial symmetry about the x- and z-axis. For the 3D MOT, the reconstructed 3D orbital has to be cylindrically symmetric.

In Silico Screening and Experimental Verification of Near‐Infrared‐Emissive Two‐Boron‐Doped Polycyclic Aromatic Hydrocarbons

AbstractEmbedding two boron atoms into a polycyclic aromatic hydrocarbon (PAH) leads to the formation of a neutral analogue that is isoelectronic to the corresponding dicationic PAH skeleton, which can significantly alter its electronic structure. Based on this concept, we explore herein the identification of near‐infrared (NIR)‐emissive PAHs with the aid of an in silico screening method. Using perylene as the PAH scaffold, we embedded two boron atoms and fused two thiophene rings to it. Based on this design concept, all possible structures (ca. 2500 entities) were generated using a comprehensive structure generator. Time‐dependent DFT calculations were conducted on all these structures, and promising candidates were extracted based on the vertical excitation energy, transition dipole moment, and atomization energy per bond. One of the extracted dithieno‐diboraperylene candidates was synthesized and indeed exhibited emission at 724 nm with a quantum yield of 0.40 in toluene, demonstrating the validity of this screening method. This modification was further applied to other PAHs, and a series of thienobora‐modified PAHs was synthesized.

In Silico Screening and Experimental Verification of Near-Infrared-Emissive Two-Boron-Doped Polycyclic Aromatic Hydrocarbons.

Embedding two boron atoms into a polycyclic aromatic hydrocarbon (PAH) leads to the formation of a neutral analogue that is isoelectronic to the corresponding dicationic PAH skeleton, which can significantly alter its electronic structure. Based on this concept, we explore herein the identification of near-infrared (NIR)-emissive PAHs with the aid of an in silico screening method. Using perylene as the PAH scaffold, we embedded two boron atoms and fused two thiophene rings to it. Based on this design concept, all possible structures (ca. 2500 entities) were generated using a comprehensive structure generator. Time-dependent DFT calculations were conducted on all these structures, and promising candidates were extracted based on the vertical excitation energy, transition dipole moment, and atomization energy per bond. One of the extracted dithieno-diboraperylene candidates was synthesized and indeed exhibited emission at 724 nm with a quantum yield of 0.40 in toluene, demonstrating the validity of this screening method. This modification was further applied to other PAHs, and a series of thienobora-modified PAHs was synthesized.

χ(2) and χ(3) enhancement by arylamine substituents in aromatic conjugated polyenyne polymers

In this work, we have determined the χ(1), χ(2), and χ(3) NLO properties of NH2substituted aromatic polyenynes in ortho, meta, and para positions. It is worth noting that Mednis-Genkin’s approximation takes into account the intraband contribution with a derivate of the dipole valence-conduction band moment transition, unlike, for example, Ward’s summation-over-sates (SOS) methodology, which considers the difference of these states. Indeed, we have selected these polymers because of the high asymmetry in their molecular wavefunction. In this way, the calculated χ(3) values of the para-NH2 substituted aromatic polyenyne with a higher degree of polymerization are near 1 X 10−7 esu. For its part, the ortho polymer has higher values, of the order of 1 X 10−6 esu, due to its high transition dipole moment. We have also found that the energy band distribution in the para position of these polymers produces van Hove points, which have a negligible proportion of the NLO properties, compared with singularity regions 1 and 2, which have a contribution of 100 %. These regions are due to the wavefunction coefficients’ first and second-order derivatives. Besides, without considering border effects nor correlation effects, and only the variation of excitation energy, we have calculated that the quaternary monomeric oligomers of these polymers have almost similar values of χ(2) and χ(3). Then, it implies building a methodology to synthesize the polymers to avoid canceling the NLO-χ(2) and -χ(3) values.

From hierarchical to matrix structure: tensions in negotiating shared leadership configurations

PurposeDespite much attention being devoted to shared leadership, the negotiation of such arrangements remains underexplored. In parallel, the revival of interest in matrix structures reveals their challenges but neglects the dynamics of shared leadership. In this case study, the author analyzes the tensions experienced by senior managers of a healthcare organization transitioning from a hierarchical to matrix structure as they negotiate their leadership roles in this new arrangement.Design/methodology/approach The author interviewed 16 senior managers, observed their meetings and analyzed documents. These data were combined with secondary data including previous interviews and observations of this top leadership team. The author then conducted an inductive data analysis.Findings The author's analysis reveals that the tensions experienced by senior managers as they negotiate their roles reflect the co-existence of leadership surpluses (too much leadership) and deficits (too little leadership) in matrix organizations. The author argues that surpluses and deficits are not mutually exclusive but are interrelated and shows how leadership surpluses can create leadership deficits.Practical implicationsThe author’s findings suggest that in contexts of leader abundance, actors should explore leadership voids. Particular attention should be paid to incidents of intrusion and exclusion, moments of transition and intense role negotiation, as those contexts are particularly conducive to leadership deficits.Originality/valueWhile previous work on matrix structures focuses on leadership surpluses, the author discusses leadership deficits. The author explores how more leaders do not necessarily mean more leadership, but instead how more leaders may result in leadership voids.

Ab initio spectroscopic studies of AlF and AlCl molecules

In this work, we report the results from our spectroscopic study on AlF and AlCl molecules. We carry out detailed electronic structure calculations in both the molecules, including obtaining the potential energy surfaces of the [Formula: see text] ground electronic state and some of the low-lying excited electronic states belonging to [Formula: see text] and [Formula: see text] symmetries. This is followed by evaluating the spectroscopic constants and molecular properties such as electric dipole moments and electric quadrupole moments. Throughout, we employ the multi-reference configuration interaction method and work with high-quality quadruple zeta basis sets. Further, transition dipole moments between the ground electronic state and singlet excited states are also studied. The relevant vibrational parameters are computed by solving the vibrational Schrödinger equation. Subsequently, the vibrational energy spacings and transition dipole moments between the vibrational levels belonging to the same electronic states are used to evaluate the spontaneous and black-body radiation-induced transition rates, followed by computing the lifetimes. Finally, the energy differences between rotational levels belonging to different vibrational levels and within an electronic state as well as the Einstein coefficients are reported.

Broadband Green Luminescence and Phase Transition in Low-Dimensional Organic-Inorganic Hybrid Iodate.

Organic-inorganic hybrid iodide systems, which can form highly ordered chromophores and uniformly oriented transition dipole moments, serve as optimal host-guest systems for the fabrication of micrometer-scale optical devices. In particular, those with low-dimensional structures can exhibit strong quantum-limited and highly localized charges, enabling the generation of high exciton energies and stable excitation emission. In this study, we report a novel instance of an organic-inorganic hybrid iodate, (C13H11N2)(IO3), which was synthesized by incorporating the optically active organic compound, 9-aminoacridine. Upon crystallization in the monoclinic space group P21/c, this compound exhibits a direct optical band gap of 2.66 eV. The incorporation of discrete organic units within the low-dimensional structures induces pronounced local charges, culminating in broadband green luminescence with a peak at 540 nm under UV excitation. This corresponds to the CIE coordinates (0.37, 0.56). A potential phase transition was inferred through a comprehensive analysis of the variable temperature structure and emission spectra. Furthermore, first-principles calculations revealed the pivotal role of organic cations in facilitating broadband luminescence.

Formulation of transition dipole gradients for non-adiabatic dynamics with polaritonic states.

A general formulation of the strong coupling between photons confined in a cavity and molecular electronic states is developed for the state-interaction state-average spin-restricted ensemble-referenced Kohn-Sham method. The light-matter interaction is included in the Jaynes-Cummings model, which requires the derivation and implementation of the analytical derivatives of the transition dipole moments between the molecular electronic states. The developed formalism is tested in the simulations of the nonadiabatic dynamics in the polaritonic states resulting from the strong coupling between the cavity photon mode and the ground and excited states of the penta-2,4-dieniminium cation, also known as PSB3. Comparison with the field-free simulations of the excited-state decay dynamics in PSB3 reveals that the light-matter coupling can considerably alter the decay dynamics by increasing the excited state lifetime and hindering photochemically induced torsion about the C=C double bonds of PSB3. The necessity of obtaining analytical transition dipole gradients for the accurate propagation of the dynamics is underlined.