Search Results (103)

Lycopene is a highly significant carotenoid in daily life, exhibiting potent antioxidant properties and recognized as one of the most powerful natural antioxidants identified in plants to date. Its functionality originates from electronic and vibrational states that exhibit a high sensitivity to environmental perturbations. Nevertheless, exclusively experimental methodologies face challenges in delivering a comprehensive molecular-level comprehension of the influence exerted by particular environmental factors on the vibronic characteristics. This deficiency in understanding hinders the accurate prediction of its behavior and functional performance within complex systems. The first principle computational investigation enables a precise elucidation of the coupling mechanisms between electronic excitations and vibrational modes under diverse solvation and interaction environments. The results indicate that the local environment significantly influences the charge distribution and orbital energies of lycopene, altering its vibrational and electronic state properties. This provides a fundamental theoretical framework for predicting their photophysical behavior and biological functions within complex matrices. Full article

Nucleic acids exhibit structured electromagnetic features shaped by classical electronegativity (EN) patterns. Mapping Pauling EN values across DNA and RNA reveals a largely invariant, high-EN phosphodiester backbone that provides a consistent electrostatic scaffold, while nucleobases introduce sequence-specific electron density shifts that generate tunable recognition fields. Together, these features create a dual-system framework in which a stable electrostatic background supports sequence-dependent informational cues. Within this environment, short-timescale vibronic interactions may arise from patterned vibrational and electronic behavior, producing modest “quantum overlay” effects compatible with known decoherence constraints. These structured, anisotropic electrostatic features may help explain differences in stability between DNA and RNA, the functional outcomes of nucleoside modifications such as N¹-methylpseudouridine (m¹Ψ), and the sensitivity of translational fidelity to small architectural perturbations. The framework yields experimentally testable predictions involving vibrational relaxation, dipole reorientation, and charge-transfer behavior, offering a classical-to-quantum interpretive bridge that may inform the design of next-generation therapeutic mRNAs. Full article

m-Aminostyrene (MAS) is a key molecular scaffold with an electron-donating amino group and a conjugating vinyl group, exhibiting significant potential in photonic materials and biological applications due to its rotamerism and photoinduced behavior. Despite its importance, a comprehensive, rotamer-resolved investigation of its vibronic and cationic spectroscopic properties is lacking. Here, we report a high-resolution study on the cis and trans rotamers of jet-cooled MAS using two-color resonant enhanced multi-photon ionization (2C-REMPI), UV-UV hole-burning (HB), and mass-analyzed threshold ionization (MATI) spectroscopies, combined with density functional theory (DFT) calculations. The HB technique unambiguously resolves the vibronic spectra of each rotamer, overcoming the limitations of previous one-color REMPI studies. The excitation energies (S₁ ← S₀) are determined to be 30,416 cm⁻¹ (cis) and 30,932 cm⁻¹ (trans). The MATI spectra yield precise adiabatic ionization energies (AIEs) of 61,569 cm⁻¹ (cis) and 61,274 cm⁻¹ (trans). A comprehensive assignment of vibrational modes in both the S₁ and D₀ states is provided, revealing distinct mode activities and frequency shifts between the two rotamers. A propensity for Δν = 0 upon ionization is observed, indicating high geometrical similarity between the S₁ and D₀ states. This work provides a crucial spectroscopic blueprint for understanding the electronic and vibrational structure of MAS rotamers, with implications for the design of functionalized styrene-based molecular systems. Full article

The identification of the chemical species responsible for the anomalous near-ultraviolet (UV) opacity in the Venusian cloud for “unknown absorber” remains a paramount challenge in planetary science. This study presents a comprehensive quantum chemical investigation into a broad suite of candidate molecules, including isomers of thiosulfeno (S₂O₂), the hydroxysulfonyl radical (HSO₃), disulfur monoxide (S₂O), disulfur dichloride (S₂Cl₂), iron(III) chloride (FeCl₃), phosphine (PH₃), and structural isomers of polysulfur oxides (S₃O). Utilizing Time-Dependent Density Functional Theory (TD-DFT) at the CAM-B3LYP/def2-TZVPP level of theory, we systematically mapped electronic transitions across three distinct environmental phases: gas-phase (without solvent), supercritical CO₂, and concentrated H₂SO₄ aerosols. To establish confidence in the predicted results, our TD-DFT approach was rigorously benchmarked against high-level theoretical methods (CCSD(T), EOM-CCSD, and MRCI+Q) from recent literature. All these electronic transitions were modeled via the Solvation Model based on Density (SMD). Our results demonstrate a profound topological and environmental dependence on spectral signatures. Among the candidates, trans-OSSO (t-OSSO) emerged as the most viable near-UV absorber candidate, exhibiting a highly allowed π → π* transition at 379.37 nm (f = 0.1140) in H₂SO₄, providing a near-perfect alignment with the observed 365 nm planetary albedo drop. Conversely, the polysulfur oxide cis-S₃O was acknowledged as a primary visible-light chromophore, with an intense absorption at 436.31 nm (f = 0.1280) responsible for the characteristic yellow tint of the planet. Additionally, the photochemically maintained SSCl₂ isomer was identified as a critical broadband near-UV absorber. Species such as S₂O and planar S₃O were found to function as critical mid-UV shields (270–300 nm). This work establishes a multi-chromophore model of the Venusian atmosphere, where a chemically stratified network of sulfur-oxygen chains and chlorine-sulfur reservoirs, tuned by the acidic aerosol matrix, collectively governs radiative balance and atmospheric super-rotation of the planet. Furthermore, to account for massive continuum tailing into the visible region (>400 nm), we employed a semi-classical Reflection Principle approach to model 1D vibronic broadening. This analysis revealed that while standard solvent effects induce minor solvatochromic shifts, ground-state structural fluxionality in the OSSO isomers drives intense, symmetry-allowed transitions deep into the visible spectrum, an effect absent in structurally constrained or rigid control species. Full article

We report a comprehensive spectroscopic investigation of p-diethynylbenzene (pDEB) using two-color resonance-enhanced multiphoton ionization (REMPI) and mass-analyzed threshold ionization (MATI) spectroscopy, complemented by density functional theory (DFT) calculations. The S₁ ← S₀ electronic origin is observed at 34,255 ± 2 cm⁻¹. The adiabatic ionization energy (IE) is determined to be 69,095 ± 5 cm⁻¹ from two-color MATI spectra recorded via the S₁ origin. Notably, a narrow peak is observed at 32 cm⁻¹ above the IE in the two-color MATI spectrum, which is assigned to a one-color, two-photon accidental resonance arising from the near-resonant condition where the S₁ ← S₀ transition energy (34,255 cm⁻¹) is close to half of the IE (69,099/2 = 34,549.5 cm⁻¹). This observation is consistent with similar reports for p-chlorofluorobenzene and p-difluorobenzene. Franck–Condon simulations show good agreement with the experimental spectra. The present results provide a spectroscopic basis for identifying pDEB and distinguishing it from its ortho and meta isomers. Full article

A microscopic model has been elaborated for the description of charge transfer-induced spin transitions in crystals containing tetranuclear Fe₂Co₂ clusters as structural units. The model takes into account the energy spectrum of each Fe₂Co₂ cluster, formed by the states arising from its initial configuration, two low-spin Fe^II and two low-spin Co^III, final configuration two low-spin Fe^III, and two high-spin Co^II, as well as the states that originate from four intermediate configurations of the type of low-spin Fe^II, low-spin Co^III, low-spin Fe^III, and high-spin Co^II. Two different types of cooperative interactions are accounted for in the model, namely, the electron–deformational coupling arising as a result of the observed elongation of the cobalt-nitrogen bonds under the low-spin Co^III$\to$ high-spin Co^II transition and the interaction via the field of phonons that originates from the coupling of the Co-ions with the full symmetric displacements of the nearest ligand surrounding, which are modulated by crystalline vibrations. The role of cooperative interactions is discussed in detail. Different types of spin transitions are predicted, including the gradual and abrupt ones as well as those manifesting hysteretic behavior. Within the framework of the developed approach, a qualitative and quantitative explanation of the experimental data on the {[(Tp*)Fe(CN)₃]₂[Co(bpy^Me)₂]₂}(OTf)₂·2DMF·H₂O compound recently reported oniere is given. Full article

The vibronic spectra of the first excited singlet state (S₁) and the cation spectra of the ground state of the cation (D₀) of jet-cooled cyclopropylbenzene (CPB) were investigated using resonance-enhanced multiphoton ionization (REMPI) and photoelectron velocity-map imaging techniques, respectively. The vibronic spectra indicated the existence of only the bisected conformer, a finding corroborated by quantum chemical calculations. The S₀ → S₁ electronic transition originated at 36,858.5 cm⁻¹, with an adiabatic ionization energy of 66,846 ± 15 cm⁻¹. Vibrational levels in both states were assigned with the assistance of theoretical geometry optimization and frequency calculations. These experimental spectra and theoretical calculations provided valuable insights into the structural and vibrational characteristics of CPB in its excited and cationic states. Full article

Thermally activated delayed fluorescence (TADF) emitters doped in host–guest systems are widely utilized for organic light-emitting diodes (OLEDs), where key rate constants and the fluorescence quantum yield (Φ_F) are strongly influenced by the surrounding environment. However, the multifaceted interactions, i.e., dipole–dipole interaction and conformational restraint between the emitter and environment have been rarely investigated systematically, where excited state charge transfer (CT) and structural relaxation (SR) of emitters should be considered equally. In this study, four representative CT–TADF emitters were selected as model systems and studied in PS/PMMA:TADF:CA host–guest doped films with varied dielectric constants and matrix rigidity. Within D–A and D–A–D configurations, donor substitution from PXZ to DMAC varied CT characteristics, whereas TRZ-based D–A and DPS-based D–A–D emitters provided a relative difference in SR owing to their different rigidity. The total reorganization energy (λ_Total) was introduced as a quantitative measure of these multifaceted interactions and correlated with the rate constants. The results indicate that the dielectric dependence of the nonradiative decay rate (k_nr^S) for D–A–D molecules cannot be explained by the simplified energy gap law, where the vibronic effect plays the role of a game changer. This work provides a quantitative framework and highlights vibrational frequency as a key design parameter for optimizing Φ_F in host–guest doped OLED devices. Full article

4-Dimethylamino-2′-hydroxy chalcone (DHC) 1 is an important natural compound that is nearly non-fluorescent in solution but highly fluorescent in its crystalline state. At room temperature, the weak fluorescence from the DHC solution is exclusively from its keto tautomer, without notable contribution from its enol tautomer. By using low-temperature fluorescence, the study found that the enol emission could be detected upon cooling with liquid N₂ in a protic solvent (e.g., EtOH). This led to observation of the fluorescence vibronic structure of enol tautomer, in addition to its enol emission λ_em ≈ 473 nm that is well separated from its keto tautomer emission (λ_em ≈ 600 nm). By freezing DHC in a solvent matrix, the study revealed the fluorescent characteristics of a single molecule in a rigid environment. Further comparison of DHC in a solvent matrix and crystalline state disclosed that the emission of crystalline DHC was primarily from the keto tautomer, along with some minor contribution from the enol tautomer, despite the tight packing environment in the crystalline state. Full article

Phenetole derivatives with dual ethoxy substituents exhibit rich conformational diversity and complex vibronic characteristics, making them important model compounds for understanding substituent effects on molecular structure and spectroscopy. In this work, we systematically investigated the stable rotamers, vibronic spectra, and cationic ground-state features of p-diethoxybenzene (PDEB) using resonance-enhanced multiphoton ionization (REMPI), UV-UV hole-burning (HB), and mass-analyzed threshold ionization (MATI) spectroscopies, combined with density functional theory (DFT) calculations. The ground-state potential energy surface (PES) of PDEB was calculated at the B3LYP/6-311++G(d,p) level, identifying eight rotamers with distinct statistical weights and relative energies. Hole-burning spectroscopy resolved two dominant rotamers (cis/up–up and trans/up–down) in the supersonic molecular beam, with their S₁←S₀ transition origins determined as 33,824 cm⁻¹ and 33,613 cm⁻¹, respectively. Franck-Condon simulations of the vibronic transitions showed excellent agreement with the experimental REMPI spectra, enabling precise assignment of substituent and benzene ring vibrational modes. MATI experiments yielded accurate adiabatic ionization energies (AIEs) of the cis and trans rotamers as 59,629 ± 5 cm⁻¹ and 59,432 ± 5 cm⁻¹, respectively, and identified active cationic vibrational modes in the D₀ state. Geometric parameters of PDEB in the S₀, S₁, and D₀ states were calculated at the B3PW91/aug-cc-pVTZ, TD-B3PW91/aug-cc-pVTZ, and UB3PW91/aug-cc-pVTZ levels, revealing structural evolution during electronic excitation and ionization. The effects of ethoxy substituent orientation on molecular energy, vibrational frequencies, and ionization energy are discussed, and differences in spectral characteristics between PDEB and its meta isomer (MDEB) are compared. This work provides a comprehensive spectral and structural database for p-diethoxybenzene and deepens the understanding of structure–property relationships in diethoxybenzene isomers. Full article

G protein-coupled receptors (GPCR) are targeted by more than one third of the clinically available drugs as specific ligands. Important as GPCR ligands may be, cases of ligand-independent GPCR activation are also abundant. In a recent article published in the journal ACS Nano, a series of cyanine skeleton-based plasmonic molecules, or molecular jackhammer, as the authors christened them, after insertion into the plasma membrane, was found after excitation by far-red light (730 nm) to vibronically-driven activate Gq-mediated calcium signaling in four different cell lines of both epithelial and muscle cell origin, which is normally activated after agonist stimulation of Gq-coupled GPCR, but the possible involvement of GPCR remains to be examined. This novel mode of activation of calcium signaling, normally associated with agonist-stimulated GPCR activation, is compared to nanoclustering activation of the neuropeptide Y2 receptor and photodynamic activation of the cholecystokinin 1 and 2 receptors. Full article

An attosecond optical pulse can entangle coherently related states of different characters, such as electronic and vibrational, in a molecular system. Using a quantum information theoretic approach, we explicitly define and discuss the surprisal of such a system in the maximal entropy formalism and identify the constraints and their conjugate Lagrange multipliers. Surprisal analysis shows how these constraints become fewer and simpler in the sudden approximation of the dynamics, a limit often valid for an ultrafast excitation. The optically accessible lower electronic states of N₂ are used as a numerical example to show the compaction of the dynamics from $\mathcal{O}\left(n^2\right)$ down to $\mathcal{O}\left(n\right)$ constraints, where $n$ is the number of vibronic states. The von Neumann entropy is used to confirm the fidelity of the compaction. Full article

In this report, a thickness-driven, aggregation–structure–transport optimum in sonicated poly(3-hexylthiophene) (P3HT) FETs was investigated. Mobility peaks at ~10–20 nm, coincident with a minimum in the photoluminescence (PL) vibronic ratio $I_{0-0}/I_{0-1}$ (strong H-aggregate interchain coupling) and X-ray diffraction sharpening of the (100) lamellar peak with slightly reduced d-spacing, indicate tighter π–π stacking and larger crystalline coherence. Absorption analysis (Spano model) is consistent with this enhanced interchain order. The mobility maximum arises from an optimal balance: J-aggregate–like intrachain planarity supports along-chain transport, while H-aggregates provide interchain connectivity for efficient hopping. Below this thickness, insufficient interchain coupling limits transport; above it, over-aggregation and disorder introduce traps and weaken gate control. The sharp rise in threshold voltage beyond the critical thickness indicates more trap states or fixed charges forming within the film bulk. As a result, a larger gate bias is needed to deplete the channel (remove excess holes) and switch the device off. These results show that electrical gating can be tuned via solution processing (sonication) and film thickness—guiding the design of P3HT devices for photovoltaics and sensing. Full article

Phenetole derivatives are widely used in various fields, and the presence of the ethoxy group, with its longer alkyl chain, suggests the possibility of multiple rotamers. In particular, diethoxybenzene derivatives, containing two ethoxy groups, exhibit an even greater number of rotameric forms. In this study, we report the first investigation of the stable structures, vibronic spectra, and cationic spectra of different rotamers of m-diethoxybenzene (MDEB). Resonance-enhanced multiphoton ionization (REMPI) spectra of the rotamers were identified via hole-burning (HB) experiments, while mass-analyzed threshold ionization (MATI) spectra provided precise adiabatic ionization energies (IEs) of the observed rotamers, as well as the active vibrations of their corresponding cations. Density functional theory (DFT) calculations predicted thirteen rotamers of MDEB, but only two rotamers were observed in the supersonic molecular beam. The band origins of the S₁ ← S₀ transition and the adiabatic IEs of the down–up and down–down rotamers of MDEB were determined to be 36,091 ± 2 cm⁻¹ and 36,165 ± 2 cm⁻¹ and 62,419 ± 5 cm⁻¹ and 63,378 ± 5 cm⁻¹, respectively. Franck–Condon spectral simulations for the S₁ ← S₀ and D₀ ← S₁ transitions were performed based on DFT calculations, and the theoretical results showed good agreement with the experimental data. Vibrational features observed in the S₁ and D₀ states were assigned by comparing the experimentally measured spectra with the simulated spectra as well as the previously reported vibrational spectra of structurally similar molecules. Finally, several key findings and molecular characteristics are discussed in detail. Full article

The mechanism by which odorants are recognized by olfactory receptors remains primarily unresolved. While charge transport is believed to play a significant role, its precise nature is still unclear. Here, we present a novel perspective by exploring the interplay between the intrinsic energy scales of odorant molecules and the gap states that facilitate intermolecular charge transport. We find that odorants act as weak tunneling conductors mainly because of the limited magnitude of electronic coupling between frontier molecular levels. This behavior is further connected to electron–phonon interaction and reorganization energy, suggesting that physically meaningful values for the latter parameter emerge only in the deep off-resonant tunneling regime. These findings complement the swipe card model of olfaction, in which an odorant needs both the right shape to bind to a receptor and the correct vibrational frequency to trigger signal transduction. Moreover, they reveal that the underlying mechanisms are much more complex than previously assumed. Full article