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The interaction between cavity photons and molecular vibrations leads to the formation of vibrational polaritons, which have demonstrated the ability to influence chemical reactivity and change material characteristics. Although ultrafast spectroscopy has been extensively applied to study vibrational polaritons, the nonlinear relationship between signal and quantum state population complicates the analysis of their kinetics. Here, we employ a second-order kinetic model and transform matrix method (TMM) to develop an effective model to capture the nonlinear relationship between the two-dimensional IR (or pump–probe) signal and excited state populations. We test this method on two types of kinetics: a sequential relaxation from the second to the first excited states of dark modes, and a Raman state relaxing into the first excited state. By globally fitting the simulated data, we demonstrate accurate extraction of relaxation rates and the ability to identify intermediate species by comparing the species spectra with theoretical ground truth, validating our method. This study demonstrates the efficacy of a second-order TMM approximation in capturing essential spectral features with up to 10% excited state population, simplifying global analysis and enabling straightforward extraction of kinetic parameters, thus empowering our methodology in understanding excited-state dynamics in polariton systems. [ABSTRACT FROM AUTHOR]

Molecular vibrations are generally responsible for chemical energy transport and dissipation in molecular systems. This transport is fast and efficient if energy is transferred by optical phonons in periodic oligomers, but its efficiency is limited by decoherence emerging due to anharmonic interactions with acoustic phonons. Using a general theoretical model, we show that in the most common case of the optical phonon band being narrower than the acoustic bands, decoherence takes place in two stages. The faster stage involves optical phonon multiple forward scattering due to absorption and emission of transverse acoustic phonons, i.e., collective bending modes with a quadratic spectrum; the transport remains ballistic and the speed can be altered. The subsequent slower stage involves phonon backscattering in multiphonon processes involving two or more acoustic phonons resulting in a switch to diffusive transport. If the initially excited optical phonon possesses a relatively small group velocity, then it is accelerated in the first stage due to its transitions to states propagating faster. This theoretical expectation is consistent with the recent measurements of optical phonon transport velocity in alkane chains, increasing with increasing the chain length. [ABSTRACT FROM AUTHOR]

A complex interplay of structural, electronic, and vibrational degrees of freedom underpins the fate of molecular excited states. Organic assemblies exhibit a myriad of excited-state decay processes, such as symmetry-breaking charge separation (SB-CS), excimer (EX) formation, singlet fission, and energy transfer. Recent studies of cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) (PDI) multimers demonstrate that slight variations in core substituents and H- or J-type aggregation can determine whether the system follows an SB-CS pathway or an EX one. However, questions regarding the relative importance of structural properties and molecular vibrations in driving the excited-state dynamics remain. Here, we use a combination of two-dimensional electronic spectroscopy, femtosecond stimulated Raman spectroscopy, and quantum chemistry computations to compare the photophysics of two PDI dimers. The dimer with 1,7-bis(pyrrolidin-1′-yl) substituents (5PDI2) undergoes ultrafast SB-CS from a photoexcited mixed state, while the dimer with bis-1,7-(3′,5′-di-t-butylphenoxy) substituents (PPDI2) rapidly forms an EX state. Examination of their quantum beating features reveals that SB-CS in 5PDI2 is driven by the collective vibronic coupling of two or more excited-state vibrations. In contrast, we observe signatures of low-frequency vibrational coherence transfer during EX formation by PPDI2, which aligns with several previous studies. We conclude that key electronic and structural differences between 5PDI2 and PPDI2 determine their markedly different photophysics. [ABSTRACT FROM AUTHOR]

The supra-molecular structure of a liquid is strongly connected to its dynamics, which in turn control macroscopic properties such as viscosity. Consequently, detailed knowledge about how this structure changes with temperature is essential to understand the thermal evolution of the dynamics ranging from the liquid to the glass. Here, we combine infrared spectroscopy (IR) measurements of the hydrogen (H) bond stretching vibration of water with molecular dynamics simulations and employ a quantitative analysis to extract the inter-molecular H-bond length in a wide temperature range of the liquid. The extracted expansivity of this H-bond differs strongly from that of the average nearest neighbor distance of oxygen atoms obtained through a common conversion of mass density. However, both properties can be connected through a simple model based on a random loose packing of spheres with a variable coordination number, which demonstrates the relevance of supra-molecular arrangement. Furthermore, the exclusion of the expansivity of the inter-molecular H-bonds reveals that the most compact molecular arrangement is formed in the range of ∼ 316 − 331 K (i.e., above the density maximum) close to the temperature of several pressure-related anomalies, which indicates a characteristic point in the supra-molecular arrangement. These results confirm our earlier approach to deduce inter-molecular H-bond lengths via IR in polyalcohols [Gabriel et al. J. Chem. Phys. 154, 024503 (2021)] quantitatively and open a new alley to investigate the role of inter-molecular expansion as a precursor of molecular fluctuations on a bond-specific level. [ABSTRACT FROM AUTHOR]

In the previous work [Reddy et al., J. Chem. Phys. 151, 044307 (2019)], we have analyzed the dynamics of the intramolecular singlet fission process in a series of prototypical pentacene-based dimers, where the pentacene monomers are covalently bonded to a phenylene linker in ortho, meta, and para positions. The results obtained were qualitatively consistent with the experimental data available, showing an ultrafast population of the multiexcitonic state that mainly takes place via a mediated (superexchange-like) mechanism involving charge transfer and doubly excited states. Our results also highlighted the instrumental role of molecular vibrations in the process as a sizable population of the multiexcitonic state could only be obtained through vibronic coupling. Here, we extend these studies and investigate the effect of the laser field on the dynamics of intramolecular singlet fission by explicitly including the coupling to the laser field in our model. In this manner, and by selectively tuning the laser field to the different low-lying absorption bands of the systems investigated, we analyze the wavelength dependence of the intramolecular singlet fission process. In addition, we have also analyzed how the nature of the initially photoexcited electronic state (either localized or delocalized) affects its dynamics. Altogether, our results provide new insights into the design of intramolecular singlet fission-active molecules. [ABSTRACT FROM AUTHOR]

Experiments have demonstrated that vibrational strong coupling between molecular vibrations and light modes can significantly change molecular properties, such as ground-state reactivity. Theoretical studies toward the origin of this exciting observation can roughly be divided into two categories, with studies based on Hamiltonians that simply couple a molecule to a cavity mode via its ground-state dipole moment on the one hand, and on the other hand ab initio calculations that self-consistently include the effect of the cavity mode on the electronic ground state within the cavity Born-Oppenheimer (CBO) approximation; these approaches are not equivalent. The CBO approach is more rigorous, but unfortunately it requires the rewriting of electronic-structure code, and its results may sometimes be hard to physically interpret. In this work, we exploit the relation between the two approaches and demonstrate on a real molecule (hydrogen fluoride) that for realistic coupling strengths, we can recover CBO energies and spectra to high accuracy using only out-of-cavity quantities from standard electronic-structure calculations. In doing so, we discover what thephysical effects underlying the CBO results are. Our methodology can aid in incorporating more possibly important features in models, play a pivotal role in demystifying CBO results, and provide a practical and efficient alternative to full CBO calculations. [ABSTRACT FROM AUTHOR]

The interaction of electronic spin and molecular vibrations mediated by spin–orbit coupling governs spin relaxation in molecular qubits. We derive an extended molecular spin Hamiltonian that includes both adiabatic and non-adiabatic spin-dependent interactions, and we implement the computation of its matrix elements using state-of-the-art density functional theory. The new molecular spin Hamiltonian contains a novel spin–vibrational orbit interaction with a non-adiabatic origin, together with the traditional molecular Zeeman and zero-field splitting interactions with an adiabatic origin. The spin–vibrational orbit interaction represents a non-Abelian Berry curvature on the ground-state electronic manifold and corresponds to an effective magnetic field in the electronic spin dynamics. We further develop a spin relaxation rate model that estimates the spin relaxation time via the two-phonon Raman process. An application of the extended molecular spin Hamiltonian together with the spin relaxation rate model to Cu(II) porphyrin, a prototypical S = 1/2 molecular qubit, demonstrates that the spin relaxation time at elevated temperatures is dominated by the non-adiabatic spin–vibrational orbit interaction. The computed spin relaxation rate and its magnetic field orientation dependence are in excellent agreement with experimental measurements. [ABSTRACT FROM AUTHOR]

We report high-level calculations of the excited states of [2,2]-paracyclophane (PCP), which was recently investigated experimentally by ultrafast pump–probe experiments on oriented single crystals [Haggag et al., ChemPhotoChem 6 e202200181 (2022)]. PCP, in which the orientation of the two benzene rings and their range of motion are constrained, serves as a model for studying benzene excimer formation. The character of the excimer state and the state responsible for the brightest transition are similar to those of the benzene dimer. The constrained structure of PCP allows one to focus on the most important degree of freedom, the inter-ring distance. The calculations explain the main features of the transient absorption spectral evolution. This brightest transition of the excimer is polarized along the inter-fragment axis. The absorption of the light polarized in the plane of the rings reveals the presence of other absorbing states of Rydberg character, with much weaker intensities. We also report new transient absorption data obtained by a broadband 8 fs pump, which time-resolve strong modulations of the excimer absorption. The combination of theory and experiment provides a detailed picture of the evolution of the electronic structure of the PCP excimer in the course of a single molecular vibration. [ABSTRACT FROM AUTHOR]

In this article, we develop a vibronic theory of clocking in molecular quantum cellular automata (QCA). The clocking mechanism is considered for a trigonal trimeric mixed-valence (MV) system with one mobile electron, which is shown to act as the dimeric unit encoding binary information (Boolean states 0 or 1) coupled to a third redox center (Null state). The model includes the electron transfer between the three centers; vibronic coupling of the mobile charge with the "breathing" modes, forming a double degenerate Jahn–Teller vibration of the molecular triangle; and two electric fields, one collinear to the dimeric unit, which controls the binary states, and the other perpendicular to this unit, performing clocking. In the framework of the adiabatic approximation, the potential surface of the trimeric system has been studied and the condition determining switching and clocking has been analyzed in terms of the two controlling fields and the vibronic and transfer parameters. A thorough understanding of the site populations is achieved through the quantum-mechanical solution of the vibronic problem, maintaining the adiabatic condition for the controlling fields. It is shown that a MV trimer can act as a molecular clocked QCA cell, with favorable conditions being a positive electron transfer parameter and sufficiently strong vibronic coupling. [ABSTRACT FROM AUTHOR]

Arising from the harmonic approximation in solving the vibrational Schrödinger equation, normal modes dissect molecular vibrations into distinct degrees of freedom. Normal modes are widely used as they give rise to descriptive vibrational notations and are convenient for expanding anharmonic potential energy surfaces as an alternative to higher-order Taylor series representations. Usually, normal modes are expressed in Cartesian coordinates, which bears drawbacks that can be overcome by switching to internal coordinates. Considering vibrational notations, normal modes with delocalized characters are difficult to denote, but internal coordinates offer a route to clearer notations. Based on the Hessian, normal mode decomposition schemes for a given set of internal coordinates can describe a normal mode by its contributions from internal coordinates. However, choosing a set of internal coordinates is not straightforward. While the Hessian provides unique sets of normal modes, various internal coordinate sets are possible for a given system. In the present work, we employ a normal mode decomposition scheme to choose an optimal set. Therefore, we screen reasonable sets based on topology and symmetry considerations and rely on a metric that minimizes coupling between internal coordinates. Ultimately, the Nomodeco toolkit presented here generates internal coordinate sets to find an optimal set for representing molecular vibrations. The resulting contribution tables can be used to clarify vibrational notations. We test our scheme on small to mid-sized molecules, showing how the space of definable internal coordinate sets can significantly be reduced. [ABSTRACT FROM AUTHOR]

Simulations of anharmonic vibrational motion rely on computationally expedient representations of the governing potential energy surface. The n-mode representation (n-MR)—effectively a many-body expansion in the space of molecular vibrations—is a general and efficient approach that is often used for this purpose in vibrational self-consistent field (VSCF) calculations and correlated analogues thereof. In the present analysis, a lack of convergence in many VSCF calculations is shown to originate from negative and unbound potentials at truncated orders of the n-MR expansion. For cases of strong anharmonic coupling between modes, the n-MR can both dip below the true global minimum of the potential surface and lead to effective single-mode potentials in VSCF that do not correspond to bound vibrational problems, even for bound total potentials. The present analysis serves mainly as a pathology report of this issue. Furthermore, this insight into the origin of VSCF non-convergence provides a simple, albeit ad hoc, route to correct the problem by "painting in" the full representation of groups of modes that exhibit these negative potentials at little additional computational cost. Somewhat surprisingly, this approach also reasonably approximates the results of the next-higher n-MR order and identifies groups of modes with particularly strong coupling. The method is shown to identify and correct problematic triples of modes—and restore SCF convergence—in two-mode representations of challenging test systems, including the water dimer and trimer, as well as protonated tropine. [ABSTRACT FROM AUTHOR]

Paramagnetic molecules with a metal ion as an electron spin center are promising building blocks for molecular qubits and high-density memory arrays. However, fast spin relaxation and decoherence in these molecules lead to a rapid loss of magnetization and quantum information. Nonadiabatic coupling (NAC), closely related to spin-vibrational coupling, is the main source of spin relaxation and decoherence in paramagnetic molecules at higher temperatures. Predicting these couplings using numerical differentiation requires a large number of computationally intensive ab initio or crystal field electronic structure calculations. To reduce computational cost and improve accuracy, we derive and implement analytical NAC and state-specific energy gradient for the ab initio parametrized crystal field Hamiltonian describing single-ion molecular magnets. Our implementation requires only a single crystal field calculation. In addition, the accurate NACs and state-specific energy gradients can be used to model spin relaxation using sophisticated nonadiabatic molecular dynamics, which avoids the harmonic approximation for molecular vibrations. To test our implementation, we calculate the NAC values for three lanthanide complexes. The predicted values support the relaxation mechanisms reported in previous studies. [ABSTRACT FROM AUTHOR]

Van der Waals clusters composed of He and aromatic molecules provide fundamental information about intermolecular interactions in weakly bound systems. In this study, phenol–helium clusters (PhOH–Hen with n ≤ 2) are characterized for the first time by UV and IR spectroscopies. The S1 ← S0 origin and ionization energy both show small but additive shifts, suggesting π-bound structures of these clusters, a conclusion supported by rotational contour analyses of the S1 origin bands. The OH stretching vibrations of the PhOH moiety in the clusters match with those of bare PhOH in both the S0 and D0 states, illustrating the negligible perturbation of the He atoms on the molecular vibration. Matrix shifts induced by He attachment are discussed based on the observed band positions with the help of complementary quantum chemical calculations. For comparison, the UV and ionization spectra of PhOH–Ne are reported as well. [ABSTRACT FROM AUTHOR]

Based on the relationship between average local ionization energy I ̄ (r) and average local electron affinity A ̄ (r) with the electronic Fukui functions, i.e., f−(r) and f+(r), respectively, in this paper, we establish a connection between nuclear and electronic Fukui functions beyond frontier molecular orbitals. As a consequence of this connection, we obtain expressions of average nuclear Fukui functions interpreted as a variation of average nucleophilicity or electrophilicity (weighted by the electronic orbital Fukui functions) with respect to nuclear displacements, which goes beyond the highest occupied molecular orbital/or lowest unoccupied molecular orbital consideration. Furthermore, from this connection and considering the frontier molecular orbital approximation, we derive expressions of nuclear Fukui functions in terms of the atom-condensed electronic Fukui functions, which imply a locality in the chemical reactivity and could be used to study the variation of local nucleophilicity or electrophilicity with respect to nuclear displacements. Finally, this new way to interpret the nuclear Fukui function could be useful in the future to study the chemical reactivity related to molecular vibrations, internal rotations, bond dissociation, chemical reaction along the model of reaction coordinate, and so on. [ABSTRACT FROM AUTHOR]

The vibrational self-consistent field (VSCF) method yields anharmonic states and spectra for molecular vibrations, and it serves as the starting point for more sophisticated correlated-vibration methods. Convergence of the iterative, non-linear optimization in VSCF calculations can be erratic or altogether unsuccessful, particularly for chemical systems involving low-frequency motions. In this work, a vibrational formulation of the Direct Inversion of the Iterative Subspace method of Pulay is presented and investigated. This formulation accounts for distinct attributes of the vibrational and electronic cases, including the expansion of each single-mode vibrational wavefunction in its own basis set. The resulting Direct Inversion of the Iterative Subspace method is shown to substantially accelerate VSCF convergence in all convergent cases as well as rectify many cases where Roothaan-based methods fail. Performance across systems ranging from small, rigid molecules to weakly bound molecular clusters is investigated in this analysis. [ABSTRACT FROM AUTHOR]

ABSTRACT Raman spectroscopy, a robust and non‐invasive analytical method, has demonstrated significant potential for monitoring biopharmaceutical production processes. Its ability to provide detailed information about molecular vibrations makes it ideal for the detection and quantification of therapeutic proteins and critical control parameters in complex biopharmaceutical mixtures. However, its application in Saccharomyces cerevisiae fermentations has been hindered by the inherent strong fluorescence background from the cells. This fluorescence interferes with Raman signals, compromising spectral data accuracy. In this study, we present an approach that mitigates this issue by deploying Raman spectroscopy on cell‐free media samples, combined with advanced chemometric modeling. This method enables accurate prediction of protein concentration and key process parameters, fundamental for the control and optimization of biopharmaceutical fermentation processes. Utilizing variable importance in projection (VIP) further enhances model robustness, leading to lower relative root mean squared error of prediction (RMSEP) values across the six targets studied. Our findings highlight the potential of Raman spectroscopy for real‐time, on‐line monitoring and control of complex microbial fermentations, thereby significantly enhancing the efficiency and quality of S. cerevisiae‐based biopharmaceutical production. [ABSTRACT FROM AUTHOR]

Efficient removal of uranium from uranium‐containing nuclear wastewater is of great significance for utilizing uranium resources and protecting the environment from uranium hazards. In this paper, a polyamidoxime‐coated coconut haustorium derived magnetic biochar (CHMBC‐PAO) composite adsorbent with excellent adsorption performance, magnetism, recyclability, and photothermal conversion properties in complex environments is prepared through a simple soak‐gelation coating method for efficient removal of uranium from nuclear wastewater. The coconut haustorium biochar, carbonized by a sponge‐like organ inside the sprouted coconut, can provide rich functional groups and electronegative surface, which are conducive to the loading of functional materials and the adsorption of uranyl, respectively. The CHMBC‐PAO presents 2.4 emu g−1 saturation magnetization, making it can be efficiently recovered through magnetic recovery. It can convert absorbed light into thermal energy through molecular thermal vibration and non‐radiative relaxation process of excitons. Enhanced by the photothermal effect, CHMBC‐PAO shows an extra high uranium adsorption capacity of 310.30 mg g−1 in acidic nuclear wastewater within a short period of time, surpassing the adsorption capacity of most reported uranium removal materials. Meanwhile, the CHMBC‐PAO also presented excellent ion selectivity and reusability. Therefore, CHMBC‐PAO composite adsorbent can be considered as a potential candidate for treating radioactive nuclear wastewater. [ABSTRACT FROM AUTHOR]

The main aim of the present study is to improve the laser frequency-doubling performance of potassium dihydrogen phosphate KDP single crystal by citric acid (CA) additive. CA-doped KDP crystals were grown unidirectionally in aqueous solutions by the temperature reduction method. CA molar percentage concentrations were 0.01, 0.05, 0.1, 0.5, and 1%, respectively. KDP seed crystals were tilted at angles of 41° and 59° from the vertical. These two values were derived from the phase-matching condition of second harmonic generation (SHG) in a KDP crystal corresponding to the 1064 nm laser. The presence of CA in the finished single crystals was demonstrated first by energy-dispersive X-ray spectroscopy. The effect of CA concentration on structural perfection, molecular vibration, optical transmission, and SHG efficiency of KDP crystals was investigated by X-ray diffraction analysis, Raman spectroscopy, ultraviolet–visible spectroscopy, and SHG measurement, respectively. The two best CA-doped KDP crystal samples, which corresponded to type I and type II phase-matching, respectively, gave a 1064 to 532 nm conversion efficiency 2.6 and 1.8 times higher than pure KDP ones. CA was shown to be a better candidate for insertion into a KDP crystal than other hydroxyl compounds and other carboxylic acids that have been reported.Please confirm if the author names are presented accurately and in the correct sequence (given name, middle name/initial, family name). Author 1 Given name: [Vinh Trung] Last name [Phan], Author 2 Given name: [Phat Thanh Nhan] Last name [Do] Also, kindly confirm the details in the metadata are correct.I confirm that the author names are correct. [ABSTRACT FROM AUTHOR]

Organic emitters that exhibit room‐temperature phosphorescence (RTP) in neat films have application potential for optoelectronic devices, bio‐imaging, and sensing. Due to molecular vibrations or rotations, the majority of triplet excitons recombine rapidly via non‐radiative processes in purely organic emitters, making it challenging to observe RTP in amorphous films. Here, a chemical strategy to enhance RTP in amorphous neat films is reported, by utilizing through‐space charge‐transfer (TSCT) effect induced by intramolecular steric hindrance. The donor and acceptor groups interact via spatial orbital overlaps, while molecular motions are suppressed simultaneously. As a result, triplets generated under photo‐excitation are stabilized in amorphous films, contributing to phosphorescence even at room temperature. The solvatochromic effect on the steady‐state and transient photoluminescence reveals the charge‐transfer feature of involved excited states, while the TSCT effect is further experimentally resolved by femtosecond transient absorption spectroscopy. The designed luminescent materials with pronounced TSCT effect show RTP in amorphous films, with lifetimes up to ≈40 ms, comparable to that in a rigid polymer host. Photoluminescence afterglow longer than 3 s is observed in neat films at room temperature. Therefore, it is demonstrated that utilizing intramolecular steric hindrance to stabilize long‐lived triplets leads to phosphorescence in amorphous films at room temperature. [ABSTRACT FROM AUTHOR]

Lanthanide‐containing organic–inorganic hybrid materials exhibit considerable potential for applications in optical devices. In this study, efficient luminescent hybrid materials are prepared by employing a straightforward doping method to mix the Eu(tta)3phen complex (tta = 2‐thenoyltrifluoroacetone, phen = 1,10‐phenanthroline) with a synthetic clay compound of hectorite (smectite). The comprehensive photophysical properties of dispersion solution containing the Eu(tta)3phen/smectite hybrid material are systematically investigated via ultraviolet‐visible absorption spectroscopy, luminescence spectra, luminescence lifetimes, and Judd–Ofelt analysis. The emission properties of the Eu(tta)3phen are enhanced by its interaction with smectite. Furthermore, the interaction suppressed the molecular vibration of Eu(tta)3phen, resulting in elevated luminescence intensity and quantum efficiency. Moreover, a highly luminescent and transparent polymeric film is prepared by incorporating Eu(tta)3phen/smectite hybrid material into a polymer (PMMA) matrix. With the addition of the smectite compound, the transparency and surface smoothness of the polymeric film are improved. Consistent with the solution state, smectite enhanced the luminescence intensity of Eu(tta)3phen in the film state. This strategy presents a novel opportunity for high‐luminescence imaging devices. [ABSTRACT FROM AUTHOR]

Excitation energy transfer (EET) is a key photoinduced process in biological chromophoric assemblies. Here we investigate the factors which can drive EET into efficient ultrafast sub-ps regimes. We demonstrate how a coherent transport of electronic population could facilitate this in water solvated NADH coenzyme and uncover the role of an intermediate dark charge-transfer state. High temporal resolution ultrafast optical spectroscopy gives a 54±11 fs time constant for the EET process. Nonadiabatic quantum dynamical simulations computed through the time-evolution of multidimensional wavepackets suggest that the population transfer is mediated by photoexcited molecular vibrations due to strong coupling between the electronic states. The polar aqueous solvent environment leads to the active participation of a dark charge transfer state, accelerating the vibronically coherent EET process in favorably stacked conformers and solvent cavities. Our work demonstrates how the interplay of structural and environmental factors leads to diverse pathways for the EET process in flexible heterodimers and provides general insights relevant for coherent EET processes in stacked multichromophoric aggregates like DNA strands. Excitation energy transfer is important for many photoinduced biological processes in systems with multiple chromophores. Here, the authors elucidate this process for the coenzyme NADH using ultrafast spectroscopy and quantum dynamics. [ABSTRACT FROM AUTHOR]

A computational methodology, founded on chemical concepts, is presented for interpreting the role of nuclear motion in the electron transport through single‐molecule junctions (SMJ) using many‐electron ab initio quantum chemical calculations. Within this approach the many‐electron states of the system, computed at the SOS‐ADC(2) level, are followed along the individual normal modes of the encapsulated molecules. The inspection of the changes in the partial charge distribution of the many‐electron states allows the quantification of the electron transport and the estimation of transmission probabilities. This analysis improves the understanding of the relationship between internal motions and electron transport. Two SMJ model systems are studied for validation purposes, constructed from a conductor (BDA, benzene‐1,4‐diamine) and an insulator molecule (DABCO, 1,4‐diazabicyclo[2.2.2]octane). The trends of the resulting transmission probabilities are in agreement with the experimental observations, demonstrating the capability of the approach to distinguish between conductor and insulator type systems, thereby offering a straightforward and cost‐effective tool for such classifications via quantum chemical calculations. [ABSTRACT FROM AUTHOR]

Although various effective machine‐learning attempts have been made to investigate the photoluminescence properties of graphene quantum dots (GQDs) or carbon dots, the physical correlation behind their mathematical models has not been reasonably elucidated. In this work, the correlation mechanism between the precursor structure and quantum yield of GQDs prepared by a "bottom‐up" method is sufficiently studied. Three decisive factors affecting the quantum yield of GQDs during the two‐component reaction system preparation are revealed, namely structure factor (F1), temperature factor (F2), and concentration factor (F3). The symmetry of precursors in the formation of sp2–sp3 hybrid carbon nanostructures is considered the key factor in the modulation of fluorescence quantum yield in GQDs. Notably, in contrast to previous work, it is first demonstrated that the normal modes of molecular vibration are the core mechanism by which the structural properties of the precursors act on the fluorescence quantum yield of GQDs. The conclusion further proved conducive in obtaining GQDs with a higher absolute quantum yield up to 83.33%. [ABSTRACT FROM AUTHOR]

Polyhydroxyalkanoates (PHAs) constitute a principal group of bio-degradable polymers that are produced by certain microbes under limited supply of nutrients. PHA is a linear polyester that comprises of 3-hydroxy fatty acid monomers. Triacylglycerol acylhydrolases are known to catalyze the hydrolysis of ester linkages and in turn they are beneficial in the degradation of PHA. In present study, lipase-catalyzed degradation of PHA synthesized by Priestia megatarium POD1 was monitored. A gene from thermotolerant Bacillus subtilis TTP-06 that was capable of expressing lipase enzyme was amplified by PCR, cloned into a pTZ57R/T-vector, transferred to an expression vector pET-23a (+) and expressed in Escherichia coli BL21 (DE3) cells. The recombinant enzyme purified to 19.37-fold had a molecular weight of 30 kDa (SDS-PAGE analysis). Scanning Electron Microscopy (SEM) revealed changes in the surface morphology of native and treated PHA films. Further, changes in molecular vibrations were confirmed by Fourier Transform Infrared Spectroscopy. [ABSTRACT FROM AUTHOR]

Copyright of Science & Technology of Food Industry is the property of Science & Technology of Food Industry Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The corrosion resistance of two multilayered metallic/ceramic coatings deposited from a 50:50 vol.% CrAl target, with a-CNx top layer deposited by High Power Impulse Magnetron Sputtering (HIPIMS) onto A11 tool steel was studied. The CrAl/CrAlN multilayer coatings with, and without a-CNx top layer, characterized by FE-SEM resulted in two different layers thicknesses of 1.5 and 1.2 µm, respectively. A glassy-like morphology was observed in the CrAl layer and in the CNx top layer, whereas the CrAlN layers exhibited a columnar morphology. XRD-analysis revealed a CrAlN FCC structure (111), accompanied of a Cr phase (110). Raman spectra for the CNx top layer, showed the characteristic peaks of G (Graphitic) and D (Disorder) for molecular vibrations in a-CNx containing thin films. Peaks were located between 1200 and 1700 cm−1. XPS results, on the other hand, showed the characteristic peaks for Cr, Al, N, present in both coatings. The deconvoluted peaks agreed with Cr2p3/2, Al2p, and N1s binding energies, respectively; besides; XRF analysis confirms the bulk chemical composition of these coatings. The electrochemical impedance, and potentiodynamic polarization tests in a 3.5 wt.% NaCl solution, displayed an improvement in the corrosion resistance for a-CNx top layer, and up to 15 times in Rp values compared to AISI A11 substrate. [ABSTRACT FROM AUTHOR]

Surface-enhanced infrared absorption (SEIRA) spectroscopy exploits the field enhancement near nanophotonic structures for highly sensitive characterization of (bio)molecules. The vibrational signature observed in SEIRA spectra is typically interpreted as field-enhanced molecular absorption. Here, we study molecular vibrations in the near field of single antennas and show that the vibrational signature can be equally well explained by field-enhanced molecular scattering. Although the infrared scattering cross section of molecules is negligible compared to their absorption cross section, the interference between the molecular-scattered field and the incident field enhances the spectral signature caused by molecular vibrational scattering by 10 orders of magnitude, thus becoming as large as that of field-enhanced molecular absorption. We provide experimental evidence that field-enhanced molecular scattering can be measured, scales in intensity with the fourth power of the local field enhancement and fully explains the vibrational signature in SEIRA spectra in both magnitude and line shape. Our work may open new paths for developing highly sensitive SEIRA sensors that exploit the presented scattering concept. The authors study molecular vibrations in the near field of single antennas, showing that the vibrational signature in SEIRA spectra can be explained by field-enhanced molecular scattering. This opens pathways for the development of sensitive SEIRA sensors exploiting this concept. [ABSTRACT FROM AUTHOR]

Nanostructure of copper doped cobalt oxide nanoparticles were synthesized by microwave irradiation assisted method. The prepared nanoparticles were further characterized by using powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and UV-Vis spectroscopy. The crystalline nature of the nanoparticles is evident from the presence of peaks in the powder X-ray diffraction pattern. The average crystallite size is found to be 20 nm calculated using Debye-Scherer formula. The different functional groups and molecular vibrations are conformed by Fourier transform infrared spectroscopy. The morphological survey of prepared nanoparticles is done by using SEM at 200 nm and 1 µm, respectively. From the micrograph we can confirm the needlelike morphology. The optical properties of nanoparticles were characterized by UV-Vis-NIR spectroscopy. From the tauc plot it is found to be 4.52 eV for indirect transition. [ABSTRACT FROM AUTHOR]

Glucose plays a key role in the regulation of the levels of blood sugar, and the body closely monitors it to maintain proper metabolic function. Although glucose is essential for human health, its excessive consumption can lead to negative effects such as obesity and diabetes. As a result, high-sensitive and accurate glucose detection is considered an essential measure in clinical analysis. Surface-enhanced Raman scattering (SERS) is an accurate method for identifying trace substances. In the present study, SERS-active substrates were used for detecting different concentrations of glucose. First, gold nanoparticles (AuNPs) were prepared by employing a chemical reduction method. Afterward, the fluorine-doped tin oxide (FTO) glass substrates were decorated with AuNPs using the electrodeposition method. Then, glucose was deposited as an analyte on SERS substrates. Interestingly, the limit of detection (LOD) of SERS-active FTO-covered glass substrates (SERS-FGS) for the detection of glucose was 10−9 M. Density functional theory (DFT) method was used to simulate and validate the Raman spectra and peak signals obtained experimentally. Moreover, the average relative standard deviation (RSD) was calculated as 3.06% for ten repeated measurements. Furthermore, the enhancement factor for these SERS-based biosensors, for the identification of molecular vibrations of 10−5 M glucose, was obtained to be 1.4310 × 104 experimentally and 1.5397 × 104 numerically. Therefore, the SERS-FGS developed in this study showed promising results for detecting glucose and controlling diseases, such as diabetes and other problems resulting from an abnormality in glucose levels. [ABSTRACT FROM AUTHOR]

Amoxicillin, an antibacterial drug commonly used in food production, requires rapid and accurate detection due to its illegal usage and potential health risks. This study focuses on the development of surface-enhanced Raman scattering (SERS) biosensors using filter paper substrates coated with silver nanoparticles (Ag NPs) for the detection of amoxicillin. The Ag NPs were prepared by employing a chemical method, and their characteristics were analyzed through various techniques. The SERS substrates exhibited an impressive limit of detection (LOD) of 10–12 M for amoxicillin, with a mean relative standard deviation (RSD) of 6.63% for repeated measurements. The experimental and simulated enhancement factors were determined as 4.044 × 104 and 2.996 × 104, respectively. These disposable, reproducible, and chemically stable substrates demonstrate great potential for SERS-based research and the development of highly sensitive biosensors. [ABSTRACT FROM AUTHOR]

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Electron transfer at electrode interfaces to molecules in solution or at the electrode surface plays a vital role in numerous technological processes. However, treating these processes requires a unified and accurate treatment of the fermionic states of the electrode and their coupling to the molecule being oxidized or reduced in the electrochemical processes and, in turn, the way the molecular energy levels are modulated by the bosonic nuclear modes of the molecule and solvent. Here we present a physically transparent quasiclassical scheme to treat these electrochemical electron transfer processes in the presence of molecular vibrations by using an appropriately chosen mapping of the fermionic variables. We demonstrate that this approach, which is exact in the limit of non-interacting fermions in the absence of coupling to vibrations, is able to accurately capture the electron transfer dynamics from the electrode even when the process is coupled to vibrational motions in the regimes of weak coupling. This approach, thus, provides a scalable strategy to explicitly treat electron transfer from electrode interfaces in condensed-phase molecular systems. [ABSTRACT FROM AUTHOR]

Silica glass has found wide applications, including space shuttle windows, optical fibers, and deep ultraviolet light lens elements, due to its excellent optical, electrical, and mechanical properties. However, understandings of its structure change under the vibration field are limited in literature. In this work, the structure of silica glass and its behavior under the vibration field have been investigated through molecular dynamics simulations. The short and medium‐range structures, including coordination number, Qn species distribution, pair distribution function, and bond angle distribution, were analyzed. It was found that the overall and local structures of silica glass showed periodic changes under the vibration field. The root‐mean‐square displacements as well as the kinetic energies of the atoms in the system were further analyzed. The results show that there is a periodic transformation of kinetic and potential energies. In addition, the kinetic energy decreases and is converted into the thermal energy during the vibration, which is confirmed by the increase of the system temperature. This can explain the thermoelastic loss mechanism in energy dissipation from literature. This work reveals the structure evolution and energy change of glass under the vibration field from atomistic level, which provides important understandings for related researches. [ABSTRACT FROM AUTHOR]

Radiative cooling is promising in meeting the current global demand for green sustainable development. However, the effective cooling of the existing radiant cooler will be limited due to the serious solar energy absorption and poor thermal insulation performance on the cold side. To addresss these issues, we propose herein a novel composite material of silicon dioxide (SiO 2) aerogel microspheres combined with polyvinylidene fluoride-cohexafluoropropylene (PVDF-HFP) nanofiber membrane, in which SiO 2 aerogel microspheres are firstly synthesized by sol-gel method and then incorporated into PVDF-HFP nanofiber membrane to give radiative cooling performance. As we expected, the molecular vibration characteristics of PVDF-HFP nanofiber membrane and the phonon polarization resonance of Si-O-Si bond in the transparent window can enhance the infrared emissivity of the membrane surface. In addition, the high porosity and the mesoporous structure formed by the interconnection of nano-network skeletons of SiO 2 aerogel microspheres determine its excellent thermal insulation performance. The as-prepared material displays that the average solar reflectance of the composite membrane is 96.07 % and the average infrared emissivity of the atmospheric window is 94.95 %. Notably, when the average solar radiation intensity is 885.56 W•m−2, the passive radiative cooling temperature during the day can reach 11.2 °C. Furthermore, this material has excellent self-cleaning and thermal insulation performance, making it a potential radiant cooling candidate in many fields. [ABSTRACT FROM AUTHOR]

In this paper, we present a comprehensive study on the 3D nanoscale topography of LaMnO 3 thin films, focusing on the influence of calcination temperature on surface morphology. The study reveals significant structural, chemical, and morphological changes as a function of the calcination temperature. XRD analysis confirmed the formation of the orthorhombic LaMnO 3 structure at 700 °C, 750 °C, and 800 °C, with increasing unit cell volume and crystallite size observed at higher temperatures. FTIR spectra identified characteristic functional groups associated with molecular vibrations, indicating the perovskite structure. SEM imaging showed grain growth with temperature, while EDS analysis confirmed compound formation and substrate interactions. AFM analysis revealed increased surface roughness with temperature, attributed to nucleation and crystal growth. Morphological and microtextural analyses further detailed changes in surface features, peaks, valleys, and voids. Fractal characterization highlighted variations in surface texture with temperature, with a decrease in dominant wavelength indicating changes in microtexture complexity. Overall, the findings provide insights into the temperature-dependent properties of LaMnO 3 thin films, essential for optimizing growth conditions and understanding their potential applications in various fields. [ABSTRACT FROM AUTHOR]

An experimental and theoretical study of the thermoluminescence (TL) of a PDHS/MCM-41 nanocomposite with the introduction of a polymer (poly-di-n-hexylsilane) (PDHS) into MCM nanopores has been carried out in the temperature range 5–150K. TL curve consists of a very narrow intense band and wider less intense band. In the nananocomposite there is a strong shift of the curve toward low temperatures compared to the curve of the film and a significant narrowing of the bands. The calculations used the model of non-adiabatic transitions. Results show a significant role of molecular vibrations in the formation of the TL curve of a nanocomposite. [ABSTRACT FROM AUTHOR]

Vibrations affect molecular optoelectronic properties, even at zero kelvin. Accounting for these effects using computational modelling is costly, as it requires many calculations at geometries distorted from equilibrium. Here, we propose a low-cost method for identifying vibrations most strongly coupled to the electronic structure, based on using orbital energy derivatives as a diagnostic. [ABSTRACT FROM AUTHOR]

The symmetry reduction of molecular shape of cationic chromophores as a design strategy to develop organic terahertz (THz) generators is used. Electron donating group (EDG) with an asymmetric shape is introduced into two types of cationic styryl‐quinolinium chromophores, leading to the development of several novel non‐centrosymmetric crystals with high macroscopic optical nonlinearity. In contrast, when an EDG with a symmetric shape is introduced, centrosymmetric crystal structure is obtained in all investigated crystals. For THz wave generation, crystals based on asymmetrically shaped EDG exhibit several optimal crystal characteristics, including a plate‐shape morphology, a large size, and an in‐plane polar axis. Furthermore, over the entire range of molecular phonon vibrations, 0.5–4 THz, the steric hindrance group in the asymmetrically shaped EDG has a strong influence on the suppression of THz phonon vibrations, leading to a low THz absorption coefficient. The crystals based on asymmetrically shaped EDG generate an ≈40 times stronger THz electric field than the inorganic ZnTe crystal and very broad THz spectra, extending up to 16 THz. Thus, the symmetry reduction of the molecular shape of cationic chromophores through the introduction of an asymmetrically shaped EDG is an effective design approach for the development of novel organic THz crystals. [ABSTRACT FROM AUTHOR]

Optical antenna resonators enable control of light‐matter interactions on the nano‐scale via electron–photon hybrid states in strong coupling. Specifically, mid‐infrared (MIR) nano‐antennas coupled to saturable intersubband transitions in multi‐quantum‐well (MQW) semiconductor heterostructures allow for the coupling strength to be tuned through antenna resonance and field intensity. Here, tip‐enhanced nano‐scale variation of antenna‐MQW coupling across the antenna is demonstrated, with a spatially‐dependent coupling strength gaq$g_{\rm aq}$ varying from 73 (strong coupling) to 24 cm−1$\rm {cm}^{-1}$ (weak coupling). This behavior is modeled based on the spatially dependent local constructive and destructive interference between tip and antenna fields. Using a quantum‐mechanical density‐matrix model of the MQW system with its designed values of transition dipole moment, doping density, and population decay time, the picosecond IR pulse coupling to intersubband transitions and the associated tip induced strong‐field saturation effects are described. These results present a new regime of nonlinear IR light‐matter control based on the dynamic manipulation of quantum hybrid states on the nanoscale and in the infrared, with a perspective regarding extension to molecular vibrations. [ABSTRACT FROM AUTHOR]

We present the study of the antibacterial properties of ZnO/CuO films, activated by LED lamp light with an emission spectrum close to that of natural sunlight, on an example of antibiotic-resistant S. aureus bacterial culture. The antibacterial properties of films with photoinduced electroporation lead to the emergence of a potential difference between semiconductor n-type ZnO and p-type CuO nanoparticles with a local increase in field intensity to a value V/cm, sufficient for irreversible electroporation to occur. Exposure leads to a decrease in bacterial contamination from the value CFU/mL to 0. Raman spectra before and after exposure were analyzed by calculating spectral peak parameters corresponding to molecular vibrations in nucleic acids, cell membranes, and proteins. The disappearance or degradation of peaks illustrating vibrations of A, G in nucleic acids, disruption of the secondary structure of proteins and the appearance of disordered forms of amide I were detected, as well as the emerging disorder of lipid chains in the membrane and the destruction of N-acetylmuramic acid and N-acetylglucosamine, which are part of the gram-positive microorganisms' cell membrane, therefore indicating the destruction of the cell wall and irreversible destruction of the internal structure of the cells. [ABSTRACT FROM AUTHOR]

Organic room temperature afterglow (ORTA) can be categorized into two key mechanisms: continuous thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP), both of which involve a triplet excited state. However, triplet excited states are easily quenched by non-radiative transitions due to oxygen and molecular vibrations. Solid-phase systems provide a conducive environment for triplet excitons due to constrained molecular motion and limited oxygen permeation within closely packed molecules. The stimulated triplet state tends to release energy through radiative transitions. Despite numerous reports on RTP in solid-phase systems in recent years, the complexity of these systems precludes the formulation of a universal theory to elucidate the underlying principles. Several strategies for achieving ORTA luminescence in the solid phase have been developed, encompassing crystallization, polymer host-guest doping, and small molecule host-guest doping. Many of these systems exhibit luminescent responses to various physical stimuli, including light stimulation, mechanical stimuli, and solvent vapor exposure. The appearance of these intriguing luminescent phenomena in solid-phase systems underscores their significant potential applications in areas such as light sensing, biological imaging, and information security. [ABSTRACT FROM AUTHOR]

In this study, the characteristics of phosphorus-doped hydrogenated amorphous silicon carbide prepared by radio-frequency glow discharge decomposition of a mixture of silane (SiH4), methane (CH4) and hydrogen (H2) were investigated. Molecular vibration, surface morphology, dark electrical conductivity, and activation energy were analyzed. The gas phase composition of CH4 was varied in the range of 0.40–0.95 relative to SiH4, while the molar fraction of phosphine (PH3) in the gas phase was adjusted from 2.75% to 10%. It was observed that the molar fraction of carbon (C) in the film affects its homogeneity, resulting in the formation of regions rich in silicon (Si) and amorphous silicon carbide (a-SixC1−x), as well as the formation of nc-Si clusters, leading to lower surface roughness. The variation in electrical properties concerning doping and the molar fraction of carbon is consistently explained in this study. [ABSTRACT FROM AUTHOR]

Phonon polaritons (PhPs) in hexagonal boron nitride enable sharp midinfrared optical resonance with strong spatial confinement, making them promising for surface‐enhanced infrared absorption (SEIRA) spectroscopy. Here, using colloidal nanosphere lithography, hBN nanopillar antennas are fabricated and their PhP resonances in a cost‐effective way are demonstrated. By varying the diameters of the hBN nanopillars, the PhP resonance can be readily tuned to match the molecular vibrations of CBP (4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl) molecules. Upon frequency matching, the coupling between the PhP resonance and the molecular vibration shows pronounced mode splitting, illustrating the SEIRA behavior with a coupling strength approaching the strong coupling regime. However, with slight frequency mismatching around 10 cm−1, the coupling strength decreases significantly, indicating a high sensitivity of the SEIRA activities to the resonance frequency of hBN nanopillar antennas. The findings provide a new method for the fabrication of PhP nanoantennas and may promote the development of PhPs in SEIRA‐based midinfrared sensing applications. [ABSTRACT FROM AUTHOR]

This research article explores the effect of chromium doping on the non-linear optical properties of strontium tungstate nanostructures. The study analyzes the samples using various techniques such as X-ray diffraction, FTIR, Raman spectroscopy, and photoluminescence studies. The results show that chromium-doped samples exhibit high non-linear absorption coefficient values, and the concentration of chromium affects the absorption behavior. The article also discusses the crystal structure, morphology, and optical properties of the doped nanostructures. The findings suggest that chromium-doped strontium tungstate nanostructures have potential applications in optical limiting and optical switching. [Extracted from the article]

The article delves into the intricate phase transitions of 1-Octadecanol and n-Nonadecane within a binary system, unveiling dynamic structural changes under varying conditions. Through Fourier transform infrared (FTIR) analysis, specific molecular vibrations were identified, shedding light on the molecular composition and interactions. The study highlights the challenges in detecting subtle phase transitions and emphasises the individuality of molecular behaviours in closely related compounds. The findings underscore the complexity of phase transitions in binary systems and advocate for a nuanced approach to studying molecular structures and behaviours. [ABSTRACT FROM AUTHOR]

Guided-mode resonance (GMR) is a compelling scheme for optical sensing of various physical quantities, which holds great promise in non-invasive detection of chemical and biological species. Current GMR sensors are mostly based on detection of environmental refractive index change, which presents a challenge for obtaining sensing selectivity as required in practical applications. In this work, we report on a prototype demonstration of using GMR for detecting molecular fingerprint absorption. In a waveguide grating made of a ZnSe layer sandwiched between a Cu film and an Au grating, a mid-infrared GMR is excited and tuned over a wide frequency range of 617.4 cm−1. Coupling of the GMR with a polydimethylsiloxane (PDMS) analyte film reveals the signature absorptions of CH2 group, whose vibrational signal is enhanced by a factor of 2.37 at a frequency detuning of 30 cm−1 between the GMR and the molecular vibration. Our theoretical analysis reveals that both near-field enhancement of GMR and its coupling strength with molecules are responsible for the molecular detection performance. These results suggest that angle-tuned GMR presents an alternative design paradigm for surface-enhanced infrared absorption spectroscopy (SEIRAS). [ABSTRACT FROM AUTHOR]

Various selective excitation methods for molecular vibrations have been developed based on the characteristics of the applied lasers. In the present work, we coherently and selectively excited molecular vibrations up to 3000 cm−1 by irradiation with a sub-10-fs laser pulse. The spectral shaping of this laser pulse enabled us to selectively excite only the target vibrational frequency range (of the model compounds acetonitrile and benzene). Furthermore, the coherent molecular vibrational dynamics were compared between selective and nonselective excitation. The coherence of the molecular vibration persisted until 2–3 ps after photoexcitation, with the lifetime of this coherence being independent of whether the coherent molecular vibration was selective or nonselective excitation. [ABSTRACT FROM AUTHOR]

Micro-wave assisted combustion synthesis technique was adopted to synthesize the dysprosium-doped yttrium calcium borate xDy3+: Y (2-x) CaB 10 O 19 (Dy:YCB) polycrystalline phosphor materials with varying concentrations (x = 1, 3, 5, 7 and 9 mol %) for the first time. The formation of phase, crystal structure was analyzed by x-ray diffraction study and was affirmed to be formed pertaining to the monoclinic crystal structure (a = 11.475 Å, b = 6.345 Å, c = 9.223 Å and α = γ = 90°, β = 91.83°) with C2 space group. The absorption capability of the prepared samples was investigated by UV-DRS spectroscopy and the optical band gap was found to be 5.28 eV. FTIR study validated the presence of functional groups and their molecular vibrations. The excitation wavelength of the synthesized samples was found to be 350 nm from photoluminescence excitation (PLE) spectra. The PL emission spectra were recorded to authenticate the emission wavelengths and found to possess two emission peaks at 480 nm (blue) and 577 nm (yellow) contributed by the Dy3+ ions. The optimized dopant concentration of dysprosium ion was fixed at x = 0.07 to avoid the concentration quenching effect. The chromaticity co-ordinate of optimized sample was determined to be x = 0.3188, y = 0.3233 which are closer to ideal white light co-ordinate. The color temperature was determined to be 6209 K, which occurs in the cool white light region. Luminous efficacy of radiation (LER) was determined to be 269.31 l m/W opt for the optimal phosphor. The luminous efficiency for the optimal phosphor was determined to be 40%. Color rendering index (CRI) of the optimal sample was evaluated to be 77. Internal quantum yield (IQE) of the optimal sample was determined to be 50.58 %. The phosphor materials have excellent thermal stability as validated from the temperature dependent PL measurements. [ABSTRACT FROM AUTHOR]

Polariton thermalization is a key process in achieving light–matter Bose–Einstein condensation, spanning from solid-state semiconductor microcavities at cryogenic temperatures to surface plasmon nanocavities with molecules at room temperature. Originated from the matter component of polariton states, the microscopic mechanisms of thermalization are closely tied to specific material properties. In this work, we investigate polariton thermalization in strongly-coupled molecular systems. We develop a microscopic theory addressing polariton thermalization through electron-phonon interactions (known as exciton-vibration coupling) with low-energy molecular vibrations. This theory presents a simple analytical method to calculate the temperature-dependent polariton thermalization rate, utilizing experimentally accessible spectral properties of bare molecules, such as the Stokes shift and temperature-dependent linewidth of photoluminescence, in conjunction with well-known parameters of optical cavities. Our findings demonstrate qualitative agreement with recent experimental reports of nonequilibrium polariton condensation in both ground and excited states, and explain the thermalization bottleneck effect observed at low temperatures. This study showcases the significance of vibrational degrees of freedom in polariton condensation and offers practical guidance for future experiments, including the selection of suitable material systems and cavity designs. [ABSTRACT FROM AUTHOR]