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A new praseodymium-based borate crystal Pr2CaB10O19 (PCB) has been grown through the high temperature solution method. PCB crystallizes in monoclinic space group C2 with unit cell parameters of a = 10.9475(10) A, b = 6.5343(7) A, c = 9.0336(8) A, β = 91.652(3)°, and Z = 2, in which B5O12 groups and PrO10 and CaO8 polyhedra constitute the three-dimensional framework. PCB exhibits a similar second harmonic response intensity to that of La2CaB10O19 and an intense orange fluorescence emission with a long fluorescence lifetime at about 610 nm excited by a xenon lamp light of 466 nm. The band gap, partial density of states, and birefringence have been investigated via theoretical calculations.

Continuous monitoring of air quality and rapid detection of pollutants are highly desirable in urban planning and development of smart cities. One of the primary greenhouse gases responsible for environmental degradation and respiratory diseases is nitrogen dioxide (NO2). Existing gas sensors for measuring NO2 concentration suffer from drawbacks such as cross-sensitivity, limited range, and short life span. On the other hand, optical sensors, in particular, surface plasmon resonance (SPR) sensors, have emerged as a preferred alternative owing to advantages like high selectivity, immunity to electromagnetic interference, and low response time. In this work, we design and simulate a NO2 sensor based on a glass waveguide coated with a gold film. Surface plasmons are excited at the interface by a 400–500-nm light source, incident at an angle of 43.16°. To enhance the sensitivity, we further coat the waveguide with three layers of carbon-silver (C–Ag) nanodots, which increases the surface plasmon field amplitude by nearly 7 times, in the absence of NO2. When NO2 concentration is varied in the range of 0–200 ppm, a corresponding change is observed in the reflected amplitude. In the absence of the C–Ag nanodots layer, the sensitivity is only 0.00042%/ppm, and on addition of C–Ag nanodots, the sensitivity increases significantly to 0.14235%/ppm which is nearly 343 times higher. These results demonstrate the efficiency of implementing nanodots in SPR sensor to detect and trace concentrations of contaminants in the gas phase.

International audience; We present a study of the O(3P) + C2H4 scattering reaction, a process that takes place in the interstellar medium and is of relevance in atmospheric chemistry as well. A comprehensive investigation of the electronic properties of the system has been carried out based on multiconfigurational ab initio CASSCF/CASPT2 calculations, using a robust and consistent active space that can deliver accurate potential energy surfaces in the key regions visited by the system. The paper discloses detailed description of the primary reaction pathways and the relevant singlet and triplet excited states at the CASSCF and CASPT2 level, including an accurate description of the critical configurations, such as minima and transition states. The chosen active space and the CASSCF/CASPT2 computational protocol are assessed against coupled-cluster calculations to further check the stability and reliability of the entire multiconfigurational procedure.

Terahertz generation and detection is the key means to explore terahertz spectrum, one of which is the application of photoconductive antenna. In this study, a low-temperature gallium arsenide (LT-...

Both the sign and intensity of photoinduced electron spin polarization (ESP) in the electronic ground state doublet (2S0/D0) of chromophore-radical complexes can be controlled by changing the nature of the metal ion. The complexes consist of an organic radical (nitronyl nitroxide, NN) covalently attached to a donor-acceptor chromophore via a m-phenylene bridge, (bpy)M(CAT-m-Ph-NN) (1) (bpy = 4,4'-di-tert-butyl-2,2'-bipyridine, M = PdII (1-Pd) or PtII (1-Pt), CAT = 3-tert-butylcatecholate, m-Ph = meta-phenylene). In both complexes, photoexcitation with visible light produces an initial exchange-coupled, three-spin (bpy•-, CAT•+ = semiquinone (SQ), and NN•), charge-separated doublet 2S1 (S = chromophore excited spin singlet configuration) excited state that rapidly decays to the ground state via a 2T1 (T = chromophore excited spin triplet configuration) state. This process is not expected to be spin selective, and only very weak emissive ESP is found for 1-Pd. In contrast, strong absorptive ESP is generated in 1-Pt. It is postulated that zero-field-splitting-induced transitions between the chromophoric 2T1 and 4T1 states (1-Pd and 1-Pt) and spin-orbit-induced transitions between 2T1 and NN-based quartet states (1-Pt) account for the differences in polarization.

Emissive properties for the cationic exciplex (A+ */D→A. D.+ ) of an isoquinolinium cation tethered to a substituted arene (1+ ) are strongly affected by hydrogen bonding solvents. At equal dielectric constant (ϵ), the ground-to-excited state energy gaps (ΔG) and solvent reorganization energies (λs ) decrease from nitriles to aliphatic alcohols. The corresponding decrease from aliphatic alcohols to high hydrogen bond acidity solvents is ∼3 times larger. The exciplex decay (kEx ), largely determined by unfolding of the exciplex to a stretched conformer, changes in a complex way depending on the strength of the hydrogen bond ability of these solvents. In contrast, the electronic couplings between the exciplex ground, excited, and charge transfer states do not show a solvent functionality dependence.

One of the rate limiting steps in catalytic ammonia synthesis is a nitrogen dissociation on a catalyst surface, which can be promoted by vibrational excitation of nitrogen molecules. In this work, the efficiency of plasma assisted heterogeneous nitrogen activation via vibrational excitation on the Ru surface is investigated. The analysis consists of two parts: in the first, ab initio calculations are performed for the adsorption and dissociation energy pathways of $${\text{N}}_{{\text{2}}}$$ on terrace and step sites and heterogeneous vibrational energy relaxation time of adsorbed nitrogen molecule is calculated using ab initio molecular dynamics. The second part includes the solution of the chemical kinetic equations for vibrationally excited molecules both in the gas phase and on the surface, and an estimation of energy cost of heterogeneous plasma activation of nitrogen. It is shown that heterogeneous vibrational energy relaxation of nitrogen molecule on the Ru surface is rather fast, and results in relatively high energy cost of vibrational nitrogen activation, which is 16 eV/molec for atmospheric pressure and 5 eV/molec for P = 4 Torr according to our calculations.

In this work, through the introduction of different lengths of alkoxy chains to the dinuclear cyclometalated platinum(II) complexes, the apparent color, solubility, luminescence properties, and self-assembly behaviors have been remarkably modulated. In the solid state, the luminescence properties have been found to arise from emission origins that switch between the 3MMLCT excited state in the red solids and the 3IL excited state in the yellow state, depending on the alkoxy chain lengths. The luminescence of the yellow solids is found to show obvious bathochromic shifts under mechanical grinding and decreased intensity under controllable hydrostatic pressure. However, the emission of the red solids exhibits both a bathochromic shift and reduced intensity due to the isotropic compression-induced shortening of the Pt···Pt and π-π distances. By combining the data obtained from X-ray diffraction (XRD), infrared (IR), and X-ray single crystal structure, a better understanding of the relationship between molecular aggregation and photophysical properties has been realized, suggesting that the length of the alkoxy chains plays an important role in governing the supramolecular assemblies.

Recently, rapid progress in the power conversion efficiency for organic solar cells (OSCs) is achieved due to the phenomenal development of the nonfullerene electron acceptors. In addition to the pairing electron donors, conjugated donor-acceptor copolymers are another key player in the high-efficiency OSCs. Here, the temporal evolution of excited states in a typical copolymer, PM6, was traced by transient absorption spectroscopy. The spectroscopic result implies the formation of two kinetically correlated intrachain species, polaron excitons and intrachain polaron pairs. In the presence of the interchain interaction, these intrachain species quickly convert into interchain polaron pairs on a time scale of few picoseconds. Our findings reveal that the electron transfer mechanisms in PM6-based OSCs substantially depend on the PM6 environment in the bulk heterojunction blends.

Dehydroergosterol (DHE, Δ5,7,9(11),22-ergostatetraen-3β-ol) is a naturally occurring fluorescent analog of cholesterol found in yeast. Since DHE has been shown to faithfully mimic cholesterol in a large number of biophysical, biochemical, and cell biological studies, it is widely used to explore cholesterol organization, dynamics and trafficking in model and biological membranes. In this work, we show that DHE, in spite of its localization at the membrane interface, does not exhibit red edge excitation shift (REES) in model membranes, irrespective of the membrane phase. These results are reinforced by semi-empirical quantum chemical calculations of dipole moment changes of DHE in ground and excited states, which show a very small change in the dipole moment of DHE upon excitation. We conclude that DHE fluorescence exhibits lack of environmental sensitivity, despite its usefulness in monitoring cholesterol organization, dynamics and traffic in model and biological membranes.

Density functional theory PBE/TZVP calculations of the geometric structures in the ground singlet state S0 and the first excited triplet state T1 were carried out for Mg pheophorbide a (MgPhe) (i.e., chlorophyll a devoid of the phytol "tail"), Mg bacteriopheophorbide a (MgBPhe), Mg chlorin (MgC), and Mg bacteriochlorin (MgBC). A comparison of the bond lengths for the pairs MgC–MgPhe and MgBC–MgBPhe found that the central macrocycle of the first pair is more unstable to splittings of equivalent bond lengths as a result of the S0 → T1 transition and as the molecular structure becomes more complex (mainly due to cyclopentanone ring V formation). The symmetry of MgC in the T1 state is lowered as compared to the C2v symmetry in the S0 state while MgBC has D2h symmetry in both states. These peculiarities are related to the central π-system of the MgC–MgPhe pair being antiaromatic (containing 24 electrons corresponding to the Huckel 4n rule) and the central π-system of the MgBC–MgBPhe pair being aromatic (containing 22 electrons corresponding to the Huckel 4n + 2 rule). The energies of the T1 states of the studied molecules are calculated. The computed $$ {E}_{T_1} $$ values for MgPhe are 11,400, 10,850, and 10,200 cm–1 for the vertical S0 → T1 transition taking into account optimization of the geometry in the T1 state and changes of the zero-point vibrations at the S0 → T1 transition, respectively, and agree well with the experimental value of 10,310 cm–1 (for chlorophyll a). The computed $$ {E}_{T_1} $$ values for MgBPhe are 8350, 8100, and 7700 cm–1 while the experimental value is 8190 cm–1 (for bacteriochlorophyll a).

Xanthophylls are a class of oxygen-containing carotenoids, which play a fundamental role in light-harvesting pigment−protein complexes and in many photoresponsive proteins. The complexity of the manifold of the electronic states and the large sensitivity to the environment still prevent a clear and coherent interpretation of their photophysics and photochemistry. In this Letter, we compare cutting-edge ab initio methods (CC3 and DMRG/ NEVPT2) with time-dependent DFT and semiempirical CI (SECI) on model keto-carotenoids and show that SECI represents the right compromise between accuracy and computational cost to be applied to real xanthophylls in their biological environment. As an example, we investigate canthaxanthin in the orange carotenoid protein and show that the conical intersections between excited states and excited−ground states are mostly determined by the effective bond length alternation coordinate, which is significantly tuned by the protein through geometrical constraints and electrostatic effects.

Experimental observations in lipid monolayers at the air-water interface have demonstrated that solitary sound pulses can be excited. These pulses propagate electrical, chemical, and thermal variations in addition to the mechanical changes in lateral pressure and lipid density, and can interact with nearby ions, polymers, and water. In addition, it was demonstrated that sound pulses that reversibly traverse the melting transition between the so-called liquid-expanded and liquid-condensed phases display unusual nonlinear properties that are strikingly similar to those of action potentials in living cells. This review describes recent experimental and theoretical investigations of sound in lipid membranes and their potential function in biology.

In this study, the B1Π excited state of NaH has been experimentally studied for the first time. Pulsed laser-induced fluorescence excitation spectroscopy was used to investigate the B1Π electronic state of NaH. A total of 48 ro-vibronic transitions were observed, including within the B-X (0-0) and B-X (0-1) transition bands. Only one B-state vibrational level was identified, and a series of PQR lines, with eight e-parity and eight f-parity sublevels (v' = 0, J' = 1-8), were assigned. The level assignment was supported by a comparison of the experimental line positions with the ab initio calculations, the dispersed laser-induced fluorescence spectrum of the NaH B1Π → X1∑+ emission, and the V-type optical-optical double resonance spectra. The Dunham-type coefficients, the mean internuclear distance, the harmonic vibrational frequency ω, and the dissociation energies D0 and De of the B1Π state were determined.

Penetration and emanation of light into tissue are limited by the strong interaction of light with the tissue components, especially oxygenated hemoglobin and white adipose tissue. This limits the possibilities for all-optical minimal invasive sensing. In order to minimize the optical losses of light in and out of the tissue, only a narrow optical window between 630 and 900 nm is available. In this work, we realized for the first time all-optical temperature sensing within the narrow optical window for tissue by using the process of triplet-triplet annihilation photon energy upconversion (TTA-UC) as a sensing tool. For this, we apply the asymmetrical benzo-fused BODIPY dye as an optimal emitter and mixed palladium benzo-naphtho-porphyrins as an optimal sensitizer. The TTA-UC sensing system is excited with λ = 658 nm with an extremely low intensity of 1 mW × cm-2 and is factual-protected for a time period longer than 100 s against oxygen-stimulated damage, allowing a stable demonstration of this T-sensing system also in an oxygen-rich environment without losing sensitivity. The sensing dyes we embed in the natural wax/natural matrix, which is intrinsically biocompatible, are approved by the FDA as food additives. The demonstrated temperature sensitivity is higher than ΔT = 200 mK placed around the physiologically relevant temperature of T = 36 °C.

The rate constants of the interactions of chromium atoms with molecular oxygen through recombination Cr + O2 + M → CrO2 + M (I) and exchange Cr + O2 → CrO + O (II) were determined by a new method for treatment of experimental data. The results, together with the available literature data, led to the following equations for the rate constants of recombination in the low-pressure limit and of the exchange reaction: $${{k}_{{1,0}}}(300 < T < 2000\,\,{\text{K}}) = {\text{ }}3.7{\text{ }} \times {\text{ }}{{10}^{{18}}}{{\left( {{T \mathord{\left/ {\vphantom {T {1000}}} \right. \kern-0em} {1000}}} \right)}^{{ - 1.49}}},$$ cm6 mol–2 s–1, $${{k}_{2}}(700 < T < 4000\,{\text{K}}) = $$ $$4.0 \times {{10}^{{14}}}{{\left( {{T \mathord{\left/ {\vphantom {T {1000}}} \right. \kern-0em} {1000}}} \right)}^{{ - 0.32}}}exp\left( { - {{4480{\kern 1pt} \,{\text{K}}} \mathord{\left/ {\vphantom {{4480{\kern 1pt} \,{\text{K}}} T}} \right. \kern-0em} T}} \right)$$ , cm3 mol‒1 s‒1. An expression for the rate constant of the reverse reaction was obtained from k2(T) and the equilibrium constant for reaction (II): $${{k}_{{ - 2}}}(700 < T < 4000\,{\text{K}}) = 3.6 \times {{10}^{{13}}}{{\left( {{T \mathord{\left/ {\vphantom {T {1000}}} \right. \kern-0em} {1000}}} \right)}^{{ - 0.64}}}$$ cm3 mol‒1 s‒1. Modeling within the framework of the RRKM theory shows that calculation of the rate constant k1,0(T) requires inclusion of not only the ground electronic state of the CrO2 molecule, but also the low-lying excited electronic states up to the dissociation threshold. A comparison of the experimental and calculated temperature dependences shows that the best agreement between them is achieved at an average portion of energy transferred in deactivating collisions of the excited CrO2 molecule with diluent gas molecules of ΔE = 2.8 kJ/mol.

The effects of discharge conditions and catalysts on CO2 methanation under the plasma were investigated via In-Situ transmission FTIR and OES analysis. The bare Al2O3, Ni/Al2O3 and Ru/Al2O3 catalysts were coated on the ZnSe window using the modified sol–gel method for In-Situ transmission FTIR analysis. It was confirmed from the OES analysis that the intensity of excited hydrogen increased in all catalysts as the discharge frequency and voltage increased, and the increment of H+ peak intensity was the largest in the Ru/Al2O3 catalyst. In addition, it was found from the In-Situ transmission FTIR analysis that the O-H band was all disappeared as the frequency and voltage increased. In conclusion, the increased H+ with the decomposition of O–H led to the increase in the CH4 conversion, resulting in the highest CH4 conversion in the Ru/Al2O3 catalyst.

Plasma-based water purification uses energetic electrons to induce chemical reactions that break down harmful contaminants into benign components. The chemical reactions needed to decompose organic chemicals and bacteria in water are driven by the production of the hydroxyl radical, OH. In this article, an atmospheric pressure plasma jet was used to produce OH and decompose methylene blue (MB) dye in water samples. The behavior of the plasma and the emission of excited OH* near the plasma–liquid interface were analyzed. Nanosecond-resolved measurements near the plasma–water interface were obtained using ICCD imaging and emissions spectroscopy synchronized to the pulsed dc power that drives plasma formation in the plasma jet. The plasma was observed to form along the front of ionization waves as “bullets” that locally produce reactive species. When the bullet hits the water surface, it rebounds and creates a secondary excitation of species at the water surface. The bouncing phenomenon increases the plasma interactions above the water surface and increases OH* excitation up to 192%. However, this increase in excitation and emission does not necessarily mean increased total OH. Higher discharge frequencies produced more OH* emission but did not change the rate of MB dye removal. Higher voltages do increase dye removal rate but with decreasing effectiveness. The results indicate that in steady state, most of the water in the gas channel has been dissociated to form OH, and each bullet merely re-excites the ground state OH (X) into OH* (A) state. A minimum operational frequency of 1 kHz was thus found to provide the best efficiency while maintaining OH production.

Summary High voltage loss (Vloss) limits further improvements of organic solar cells (OSCs), and thus developing effective approaches to reduce Vloss is important. Herein, a solvent additive strategy was employed to reduce Vloss in PM6:L8-BO OSCs. The use of diiodomethane (DIM) instead of 1,8-diiodooctane (DIO) led to a reduction in energetic difference between the single excited state of L8-BO and the charge transfer state in PM6:L8-BO blend, and thereby a reduced Vloss. Meanwhile, the morphology, charge transport property, and quantum efficiency are not deteriorated. Consequently, the DIM-processed OSCs showed a high power conversion efficiency (PCE) of 18.60% (certified as 18.20%) with a high Voc of 0.893 V, higher than those (PCE = 18.23%, Voc = 0.869 V) of the DIO-processed devices, representing the highest efficiency for binary OSCs thus far. DIM has also been successfully applied in PM6:BTP-eC9 and PM6:3TP3T-4F blends, and high PCEs with reduced Vloss were also achieved.

Allosteric pluripotency arises when an allosteric effector switches from agonist to antagonist depending on the experimental conditions. For example, the Rp-cAMPS ligand of Protein Kinase A (PKA) switches from agonist to antagonist as the MgATP concentration increases and/or the kinase substrate affinity or concentration decreases. Understanding allosteric pluripotency is essential to design effective allosteric therapeutics with minimal side effects. Allosteric pluripotency of PKA arises from divergent allosteric responses of two homologous tandem cAMP-binding domains, resulting in a free energy landscape for the Rp-cAMPS-bound PKA regulatory subunit R1a in which the ground state is kinase inhibition-incompetent and the kinase inhibition-competent state is excited. The magnitude of the free energy difference between the ground non-inhibitory and excited inhibitory states (ΔGR,Gap) relative to the effective free energy of R1a binding to the catalytic subunit of PKA (ΔGR:C) dictates whether the antagonism-to-agonism switch occurs. However, the key drivers of ΔGR,Gap are not fully understood. Here, by analyzing an R1a mutant that selectively silences allosteric pluripotency, we show that a major determinant of ΔGR,Gap unexpectedly arises from state-selective frustration in the ground inhibition-incompetent state of Rp-cAMPS-bound R1a. Such frustration is caused by steric clashes between the phosphate-binding cassette and the helices preceding the lid, which interact with the phosphate and base of Rp-cAMPS, respectively. These clashes are absent in the excited inhibitory state, thus reducing the ΔGR,Gap to values comparable to ΔGR:C, as needed for allosteric pluripotency to occur. The resulting model of allosteric pluripotency is anticipated to assist the design of effective allosteric modulators., The Rp-cAMPS ligand of protein kinase A switches from agonist to antagonist depending on metabolite and proteomic contexts. We show that the state-selective frustration is a key driver of this allosteric pluripotency phenomenon.

Yb:CaWO4 and Yb, Nb:CaWO4 single crystals have been grown by the Czochralski method in air and in protective atmospheres and subjected to additional annealing in air, in CO/CO2 atmosphere, and in forevacuum. The optical absorption spectra in the range from 250 to 1500 nm and the luminescence spectra of these crystals in the visible and near-IR spectral regions upon UV excitation have been investigated. It is shown that additional introduction of Nb5+ ions into Yb:CaWO4 crystal increases by an order of magnitude (almost to unity) the Yb3+ distribution coefficient between CaWO4 crystal and melt. It is found that optical excitation of the crystals in the range of 260–355 nm induces down-conversion luminescence of Yb3+ ions from the 2F5/2 level in the vicinity of 1 µm. An increase in the oxidative potential of synthesis atmosphere, as well as the introduction of niobium into the crystal composition, weakens this luminescence. A consistent pattern explaining the nature of the donor centers involved in down-conversion population of excited state 2F5/2 of Yb3+ in the crystals is proposed. Within this pattern, Yb2+ ions play the role of these donor centers. Another (much less efficient) mechanism of population of the 2F5/2 level is intracenter relaxation from the higher-lying charge transfer excited state within Yb3+ ions. At the same time, it is confirmed that color centers based on oxygen vacancies and partially reduced tungsten ions, as well as self-trapped excitons on tungstate complexes, are not involved in population of the excited state 2F5/2 of Yb3+ ions, and the optical centers formed in Yb:CaWO4 crystals as a result of vacuum annealing suppress ytterbium luminescence.

In the present study Eu2O3 doped Li2O–Si2O–B2O3 glasses (LSBE) were synthesized by the melt quench technique. The physical, thermal, and spectroscopic properties of prepared glasses by various techniques have been investigated in this work. The powder X-ray diffraction study confirms the amorphous nature of glass samples. The various absorption bands assigned were observed from ground level 7F0 to various excited states within the 4f shell. Emission spectra exhibit bands in the visible region from 450 to 750 nm. The spectra show some sharp peaks belongs to 4f electronic transitions of Eu3+ ion at 5D0 → 7F0 (578 nm), 5D0 → 7F1 (590 nm), 5D0 → 7F2 (614 nm), 5D0 → 7F3 (652 nm), and 5D0 → 7F4 (701 nm). The band at 614 nm corresponds to 5D0 →7F2 transition is hypersensitive among all bands. From the CIE chromaticity diagram, the glass sample LSBE-5 shows the highest emission intensity with color coordinates x = 0.56, y = 0.33 among all glass samples.

Photoinduced symmetry-breaking charge separation (SB-CS) processes offer the possibility of harvesting solar energy by electron transfer between identical molecules. Here, we present the first case of direct observation of bimolecular SB-CS in a transition metal complex, [(FeL2)-L-III](PF6) (L = [phenyl(tris(3-methylimidazol-1-ylidene))borate](-)). Photoexcitation of the complex in the visible region results in the formation of a doublet ligand-to-metal charge transfer ((LMCT)-L-2) excited state (E0-0 = 2.13 eV), which readily reacts with the doublet ground state to generate charge separated products, [(FeL2)-L-II] and [(FeL2)-L-IV](2+), with a measurable cage escape yield. Known spectral signatures allow for unambiguous identification of the products, whose formation and recombination are monitored with transient absorption spectroscopy. The unusual energetic landscape of [(FeL2)-L-III](+), as reflected in its ground and excited state reduction potentials, results in SB-CS being intrinsically exergonic (Delta G(CS)degrees similar to -0.7 eV). This is in contrast to most systems investigated in the literature, where Delta C-CS degrees is close to zero, and the charge transfer driven primarily by solvation effects. The study is therefore illustrative for the utilization of the rich redox chemistry accessible in transition metal complexes for the realization of SB-CS.

The unimolecular dissociation dynamics of the C6H6-C6Cl6 (Bz-HCB) complex is studied with initial excitation of all vibrational modes for a temperature range of 1000-2000 K and with mode-specific excitations at 1500 K. The results are compared with those of the C6H6-C6F6 [Bz- HFB] complex. When all modes of Bz-HCB are initially excited, the rate of dissociation is slower with respect to Bz-HFB. However, the rate of dissociation is faster when simulations with nonrandom excitation of the specific vibrational modes are performed. The rate of dissociation of Bz-HCB is found to become slower when a few intramolecular modes are excited along with all inter-fragment modes compared to the simulation when only inter-fragment modes of the same complex are excited. Such an energy-transfer dynamics is absent if both intramolecular and inter-fragment modes are not initially excited. Thus, a "stimulated" resonance energy-transfer dynamics is observed in Bz-HCB dissociation dynamics.

CdSe quantum dots are the most studied Cd-based quantum dots with their high quantum yield, high photostability, narrow emission band, and easy synthesis procedure. They are frequently used to develop light emitting diode (LED) due to their unique photophysical properties; however, their narrow emission band causes a challenge to design white LEDs because white light emission requires emission in multiple wavelengths with broad emission bands. Here in this study, we developed CdSe quantum dots with a narrow band-edge emission band and broad defect-state emission band through a modified two-phase synthesis method. Our results revealed that defect-state emission is directly linked to the surface of quantum dots and can be excited through exciting surfactant around the quantum dot. The effect of surfactant on emission properties of CdSe quantum dots diminished upon growing a shell around CdSe quantum dots; as a result, surface-dependent defect-state emission cannot be observed in gradient heterogeneous alloyed CdSxSe1-x quantum dots.

Ruthenium(II) complexes, like [(tbbpy)2Ru(dppz)]2+ (Ru-dppz; tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine, dppz = dipyrido-[3,2-a:2',3'-c]phenazine), have emerged as suitable photosensitizers in photoredox catalysis. Since then, there has been ongoing interest in the design of π-extended Ru-dppz systems with red-shifted visible absorption maxima and sufficiently long-lived excited states independent of the solvent or pH value. Herein, we explore the photophysical properties of protonation isomers of the linearly π-extended [(tbbpy)2Ru(L)]2+-type complexes bearing a dppz ligand with directly fused imidazole (im) and methyl-imidazole units (mim) as L. Steady-state UV-vis absorption, resonance Raman, as well as time-resolved emission and transient absorption spectroscopy reveal that Ru-im and Ru-mim show desirable properties for the application in photocatalytic processes, i.e., strong visible absorbance and two long-lived excited states in the 3ILCT and 3MLCT manifold, at pH values between 3 and 12. However, protonation of the (methyl-)imidazole unit at pH ≤ 2 unit causes decreased excited-state lifetimes and an emission switch-off.

Developing highly active catalysts for hydrogen evolution reaction is vital for large-scale and efficient production of hydrogen through water splitting. In this study, we reported scale-up TiO2/LaFeO3 composite catalysts with multiple heterojunctions synthesized via facile solid-phase reaction and investigated their hydrogen evolution reaction (HER) performance in both acidic and alkaline solutions. To be excited, under AM1.5 simulated sunlight irradiation, the working electrode decorated by TiO2/LaFeO3 presents a higher current density with 10 mV/cm2 at 0.55 V in a 0.5 M H2SO4 solution, suppressing the corresponding performance with the occasion of pure electrocatalysis. Importantly, the hydrogen evolution efficiency can reach 7.62 mmol h−1 cm−2, overwhelming approximately 5.3 times higher than that of commercial P25 (1.43 mmol h−1 cm−2) with exceptional stability via imposing simulated sunlight and a bias of 500 mV. Therefore, such excellent catalysts could serve as an alternative to reach remarkable HER performance via fossil fuels free technology, potentially making contribution toward the goal of global “carbon neutral” by 2050.

Recently, a new production process of various metals and alloys from their oxides and ores by Cold Hydrogen Plasma (CHP) has been introduced. CHP is produced by using a microwave oven, using less power than the microwave ovens used domestically for cooking food. CHP is very efficient in producing metals and alloys from their oxides because of excited species. These excited species decrease the thermodynamic and kinetic barriers of reduction, making the reduction easier and faster. In the current investigation, nickel has been produced from nickel oxide (NiO) pellets of ~ 2.5 gm to ~ 7.5 gm. The hydrogen flow rate ranges from 70 ml/s to 150 ml/s, and power varies from 600 to 750 W. The time taken for reduction changed between 300 to 1200 s. CHP reduces very fast due to the active oxygen present in it. This faster production of nickel from pellets upto ~ 7.5 gm at such low power opens up the possibilities of upscaling the reduction of NiO by CHP.

When ionic dyes are close together, the internal Coulomb interaction may affect their photophysics and the energy-transfer efficiency. To explore this, we have prepared triangular architectures of three rhodamines connected to a central triethynylbenzene unit (1,3,5-tris(buta-1,3-diyn-1-yl)benzene) based on acetylenic coupling reactions and measured fluorescence spectra of the isolated, triply charged ions in vacuo. We find from comparisons with previously reported monomer and dimer spectra that while polarization of the π-system causes redshifted emission, the separation between the rhodamines is too large for a Stark shift. This picture is supported by electrostatic calculations on model systems composed of three linear and polarizable ionic dyes in D3h configuration: The electric field that each dye experiences from the other two is too small to induce a dipole moment, both in the ground and the excited state. In the case of heterotrimers that contain either two rhodamine 575 (R575) and one R640 or one R575 and two R640, emission is almost purely from R640 although the polarization of the π-system expectedly diminishes the dipole-dipole interaction.

Photodynamic therapy (PDT) involving the generation of cytotoxic reactive oxygen species under light in the presence of sufficient oxygen has been widely used in diagnosing and treating cancer. However, the ubiquitous hypoxia in many solid tumors due to their abnormal proliferation and vascularization has greatly compromised the therapeutic effect. We have designed and prepared a tumor therapeutic nanoplatform for improving PDT based on defective TiO[Formula: see text] (d-TiO[Formula: see text] with the consideration that the continuous PDT would cause hypoxic tumor microenvironment (HTM) in which many hypoxia-sensitive drugs might be activated to exert the antitumor activities. The inorganic d-TiO[Formula: see text] nanoparticles (NPs) were firstly prepared and then modified by APTES to obtain the mesoporous d-TiO[Formula: see text]@SiO2NPs. The organic photosensitizer pyropheophorbide-a (PPa) and hypoxic-sensitive agent 6-aminoflavone (AF) were then adsorbed in the mesoporous SiO2, followed by further hydrophilic PEGylation to improve the biocompatibility. Defective d-TiO[Formula: see text] and the PPa could simultaneously consume oxygen after light excitation, while the resulted HTM was utilized to activate the hypoxic-sensitive agent 6-aminoflavone (AF) to trigger anti-cancer effect. The prepared d-TiO[Formula: see text]@SiO2/PPa/AF@PEG NPs were stable in normal physiological environment, and could continuously release PPa and AF under slightly acidic conditions. The in vitro experiments against cancer cells suggested that the combination of PPa and AF displayed significantly enhanced antitumor activities than that of monotherapy. Therefore, this research offered a potential application for 6-aminoflavone in PDT-induced hypoxia to improve the antitumor effects.

Ultrafast excited-state dynamics of CuBr3- complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr3- complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.6 and 7.3 ps in acetonitrile and dichloromethane, respectively. Internal conversion of the LF state is accompanied by vibrational relaxation that occurs on the same time scale. Based on the analysis of coherent oscillations and quantum-chemical calculations, the predominant forms of the CuBr3- complex in acetonitrile and dichloromethane solutions were revealed. In acetonitrile, the CuBr3- complex exists as [CuBr3(CH3CN)2]-, whereas three forms of this complex, [CuBr3CH2Cl2]-, [CuBr3(CH2Cl2)2]-, and [CuBr3(CH2Cl2)3]-, are present in equilibrium in dichloromethane.

Herein, the ultrafast photoinduced dynamics and vibrational coherences for two perylenebisimide (PBI) H-aggregates showcase the formation of the excimer state and the delocalized radical anion state in the excited state, respectively. Using femtosecond transient absorption (fs-TA) and time-resolved impulsive stimulated Raman scattering (TR-ISRS) measurements, we unveiled excited-state dynamics of PBI H-aggregates in two aspects: (1) the intermolecular interactions between PBI units in H-aggregates induce the formation of new excited states, excimer and delocalized radical anion states, and (2) the intermolecular out-of-plane along the aggregate axis and the PBI core C═C stretch Raman modes can be a crucial indicator to understand the coherent exciton dynamics in H-aggregates. Notably, those excited-state Raman modes showed stationary peak positions during the excited-state dynamics. TR-ISRS analysis provides insights into the excited-state vibrational coherences concerning the formation of the excimer and charge-delocalized state in each aggregate system.

3-Hydroxyflavon (3-HF) represents an interesting paradigmatic compound to study excited-state intramolecular proton transfer (ESIPT) and intermolecular (ESInterPT) processes to explain the experimentally observed dual fluorescence in solvents containing protic contamination (water) as opposed to single fluorescence in highly purified nonpolar solvents. In this work, adiabatic on-the-fly molecular dynamics simulations have been performed for isolated 3-HF in an aqueous solution using a polarizable continuum model and including explicit water molecules to represent adequately hydrogen bonding. For the calculation of the excited state, time-dependent density functional theory and the Becke-3-Lee-Yang-Parr (B3LYP) functional have been used. For the isolated 3-HF, ultrafast ESIPT from the enol group to the neighboring keto group has been observed. The calculated PT time of 48 fs agrees well with the experimental value of 39 fs. Addition of one water molecule quenches this ESIPT process but shows an intermolecular concerted or stepwise tautomerization process via the bridging water molecule. Adding a second or more water molecules inhibits this ESInterPT process to a large degree. Most of the trajectories do not show any PT, preserving the initial excited-state enol structure, which is the origin of the violet-blue fluorescence appearing in the solvents contaminated with protic components.

A series of new naphthalimide and phenothiazine-based push–pull systems (NPI-PTZ1–5), in which we structurally modulate the oxidation state of the sulfur atom in the thiazine ring, i.e., S(II), S(IV), and S(VI), was designed and synthesized by the Pd-catalyzed Sonogashira cross-coupling reaction. The effect of the sulfur oxidation state on the spectral, photophysical, and electrochemical properties was investigated. The steady-state absorption and emission results show that oxygen functionalization greatly improves the optical (absorption coefficient and fluorescence efficiency) and nonlinear optical (hyperpolarizability) features. The cyclic voltammetry experiments and the quantum mechanical calculations suggest that phenothiazine is a stronger electron donor unit relative to phenothiazine-5-oxide and phenothiazine-5,5-dioxide, while the naphthalimide is a strong electron acceptor in all cases. The advanced ultrafast spectroscopic measurements, transient absorption, and broadband fluorescence up conversion give insight into the mechanism of photoinduced intramolecular charge transfer. A planar intramolecular charge transfer (PICT) and highly fluorescent excited state are populated for the oxygen-functionalized molecules NPI-PTZ2,3 and NPI-PTZ5; on the other hand, a twisted intramolecular charge transfer (TICT) state is produced upon photoexcitation of the oxygen-free derivatives NPI-PTZ1 and NPI-PTZ4, with the fluorescence being thus significantly quenched. These results prove oxygen functionalization as a new effective synthetic strategy to tailor the photophysics of phenothiazine-based organic materials for different optoelectronic applications. While oxygen-functionalized compounds are highly fluorescent and promising active materials for current-to-light conversion in organic light-emitting diode devices, oxygen-free systems show very efficient photoinduced ICT and may be employed for light-to-current conversion in organic photovoltaics.

Nonadiabatic effects are ubiquitous in photophysics and photochemistry, and therefore, many theoretical developments have been made to properly describe them. Conical intersections are central in nonadiabatic processes, as they promote efficient and ultrafast nonadiabatic transitions between electronic states. A proper theoretical description requires developments in electronic structure and specifically in methods that describe conical intersections between states and nonadiabatic coupling terms. This review focuses on the electronic structure aspects of nonadiabatic processes. We discuss the requirements of electronic structure methods to describe conical intersections and nonadiabatic couplings, how the most common excited state methods perform in describing these effects, and what the recent developments are in expanding the methodology and implementing nonadiabatic couplings.

A full three-dimensional global potential energy surface (PES), covering the whole configuration space, is reported first for the title system by fitting high-level ab initio energies at the multireference configuration interaction level with the aug-cc-pV6Z basis set. In this work, the many-body expansion method is invoked to fit the innate character of the CH2+(12A″) PES. The topographical features are examined in detail based on the new global PES and in accordance with the other calculations from the ab initio energies, which show the correct behavior at the C+(2P) + H2(X1Σg+) and CH+(a3Π) + H(2S) dissociation limits. Using a time-dependent wave packet method, we provide insights into the dynamics behavior for reaction of C+(2P) + H2(X1Σg+) → CH+(a3Π) + H(2S). The integral cross sections and reaction probabilities increase monotonically in terms of the collision energy.

A powerful and attractive route to develop novel photocatalysts for C-N bond formation involves the use of pyrrolidine as the substrate and cocatalyst simultaneously. Herein, a new polyoxometalate (POM)-based metal-organic framework, namely, [Ni6(OH)3(H2O)9(DPNDIH)(SiW9O34)]2·2H2O (SiW9Ni6-DPNDI) (DPNDI = N,N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide), was prepared by incorporating a Ni6 cluster-substituted POM anion and a photosensitizer (DPNDI) into a framework. The anion···π interactions and covalent bonds between SiW9Ni6 and DPNDI are beneficial for the consecutive electron separation and transfer. Under visible-light irradiation, DPNDI can be easily excited to generate radical species DPNDI* that could be further excited in the presence of the electron donor pyrrolidine for the inert O2 activation. SiW9Ni6-DPNDI showed a high efficiency in the photocatalysis of C-N bond formation under a mild condition by the synergy of DPNDI and SiW9Ni6. The results of the reaction were confirmed by gas chromatography and 1H NMR. In addition, SiW9Ni6-DPNDI exhibited a high sustainability without an obvious change in yields after five cycles.

In the current study, we present nonadiabatic (NAMD) and adiabatic molecular dynamics simulations of the transition-state dynamics of photoexcited cyclooctatetraene (COT). The equilibrium-state structure and absorption spectra are analyzed using the semiempirical Austin Model 1 potential. The NAMD simulations are obtained by a surface-hopping algorithm. We analyzed in detail an active excited to ground state relaxation pathway accompanied by an S2/S3(D2d) → S1(D8h) → S0(D4h) → S0(D2d) double-bond shifting mechanism. The simulated excitation lifetime is in good agreement with experiment. The first excited singlet state S1 plays a crucial role in the photochemistry. The obtained critical molecular conformations, energy barrier, and transition-state lifetime results will provide a basis for further investigations of the bond-order inversion and photoswitching process of COT.

Two sulfonate ester derivatives of anthraquinone, 1-tosyloxy-2-methoxy-9,10-anthraquinone (1a) and 1-trifluoromethylsulfonoxy-2-methoxy-9,10-anthraquinone (1b) were prepared and their ability to produce strong acids upon photoexcitation was examined. It is shown that these compounds generate acid with a yield that increases with light intensity when the applied photon dose is held constant. Additional experiments show that the rate of acid generation increases 4 fold when visible light (532 nm) laser pulses are combined with ultraviolet (355 nm) compared with ultraviolet alone. Continuous wave diode laser photolysis also effects acid generation with a rate that depends quadratically on the light intensity. Density functional theory calculations, laser flash photolysis, and chemical trapping experiments support a mechanism whereby an initially formed triplet state (T1) is excited to a higher triplet state which in turn undergoes homolysis of the RS(O2)–OAr bond. Secondary reactions of the initially formed sulfonyl radicals produce strong acids. It is demonstrated that high intensity photolysis of either 1a or 1b can initiate cationic polymerization of ethyl vinyl ether.

The detailed excited-state intermolecular proton transfer (ESInterPT) mechanism of 2,7-diazaindole with water wires consisting of either one or two shells [2,7-DAI(H2O)n; n = 1-5] has been theoretically explored by time-dependent density functional theory using microsolvation with an implicit solvent model. On the basis of the excited-state potential energy surfaces along the proton transfer (PT) coordinates, among all 2,7-DAI(H2O)n, the multiple ESInterPT of 2,7-DAI(H2O)2+3 through the first hydration shell (inner circuit) is the most easy process to occur with the lowest PT barrier and a highly exothermic reaction. The lowest PT barrier resulted from the outer three waters pushing the inner circuit waters to be much closer to 2,7-DAI, leading to the enhanced intermolecular hydrogen-bonding strength of the inner two waters. Moreover, on-the-fly dynamic simulations show that the multiple ESInterPT mechanism of 2,7-DAI(H2O)2+3 is the triple PT in a stepwise mechanism with the highest PT probability. This solvation effect using microsolvation and dynamic simulation is a cost-effect approach to reveal the solvent-assisted multiple proton relay of chromophores based on excited-state proton transfer.

The synthesis and properties of dinaphthotropone bisimide (DNTrBI) and dinaphthocycloheptatriene bisimide (DNCHepBI) are described. Their molecular design is conceptually based on the insertion of a carbon atom into a perylene bisimide (PBI) core. These molecules adopt non-planar structures due to the presence of a seven-membered ring. The PBI derivative into which a carbonyl group was inserted (DNTrBI) immediately underwent nonradiative decay and/or intersystem crossing in its excited state. The PBI derivative into which a methylene group was inserted (DNCHepBI) was susceptible to deprotonation on account of the two electron-withdrawing naphthalene monoimide units. Subsequent aerobic oxidation resulted in the formation of a C−C bond at the central methylene unit, thus affording a σ-dimer. The formation of this C−C bond is dynamically redox-active, i.e., electron injection into the σ-dimer almost quantitatively regenerated the deprotonated DNCHepBI.

Rare-earth (RE)-doped tungstate LiSrGd1−x(WO4)3:xEu red-emitting phosphors were prepared by traditional high-temperature solid-state reaction method. These samples were characterized by X-ray diffraction, scanning electron microscopy, and photoluminescence (PL). PL spectrum exhibited characteristic luminescent 5D0/7FJ (J = 0–4) intra-4f shell Eu3+ ion transitions. Eu3+-activated LiSrGd(WO4)3 phosphors could be excited by near-ultraviolet (NUV) light of 393 nm and blue light of 464 nm and showed excellent red emission lying around 616 nm (5D0 → 7F2). Eu3+-doped concentration in LiSrGd1−x(WO4)3:xEu was x = 0.3. Arising temperature to 393 K, the red emission intensity of LiSrGd1−x(WO4)3:xEu phosphor decayed by only 13.57 and 19.53 $$\%$$ relative to room temperature, which indicates that the phosphor possesses good temperature stability. The evaluated Commission International de l’Eclairage (CIE) color coordinates of these phosphors were close to the standard red CIE color coordinate published by the National Television Systems Committee. Hence LiSrGd1−x(WO4)3:xEu phosphor is promising with potential for white LED.

The optical properties of two Re(CO)3(bpy)Cl complexes in which the bpy is substituted with two donor (triphenylamine, TPA, ReTPA2) as well as both donor (TPA) and acceptor (benzothiadiazole, BTD, ReTPA-BTD) groups are presented. For ReTPA2 the absorption spectra show intense intraligand charge-transfer (ILCT) bands at 460 nm with small solvatochromic behavior; for ReTPA-BTD the ILCT transitions are weaker. These transitions are assigned as TPA → bpy transitions as supported by resonance Raman data and TDDFT calculations. The excited-state spectroscopy shows the presence of two emissive states for both complexes. The intensity of these emission signals is modulated by solvent. Time-resolved infrared spectroscopy definitively assigns the excited states present in CH2Cl2 to be MLCT in nature, and in MeCN the excited states are ILCT in nature. DFT calculations indicated this switching with solvent is governed by access to states controlled by spin-orbit coupling, which is sufficiently different in the two solvents, allowing to select out each of the charge-transfer states.

A set of gold corrole complexes containing four different β-substituent groups (Br/I/CF3), namely, 4Br-Au, 4I-Au, and 4CF3-Au, were investigated; all showed room temperature phosphorescence. The phosphorescence quantum yields of the corroles were determined using tetraphenylporphyrin as a reference: Φph (4I-Au, 0.75%) > Φph (4Br-Au, 0.64%) > Φph (4CF3-Au, 0.38%). 4CF3-Au exhibited near-IR emission (858 nm, aerobic); absorbance intensity for the Q-band was higher than that for the Soret band. Complex 4I-Au showed a longer phosphorescence lifetime (82 μs) compared to those of 4Br-Au (53 μs) and 4CF3-Au (28 μs; N2, tol). Thermally activated delayed fluorescence (TADF) emission of 4I/Br-Au complexes was observed: stronger emission intensity correlated with increasing temperature. Good negative correlations for 4I/Br-Au were observed between the Soret band absorption energy and the solvent polarizability: excited states of 4I/Br-Au are more polar than their ground states. TD-DFT calculations revealed very fast intersystem crossing (ISC) rate constants, 2.20 × 1012 s-1 (4CF3-Au) > 1.96 × 1011 s-1 (4Br-Au) > 1.15 × 1011 s-1 (4I-Au), and importantly, the reverse intersystem crossing (rISC) rate constants are determined as 1.68 × 107 s-1 (4I-Au) > 2.40 × 103 s-1 (4Br-Au) ≫ 8.09 × 10-8 s-1 (4CF3-Au). The exceptionally low rISC rate constant of 4CF3-Au is attributed to its more steric and deformed structure bearing a larger energy gap between the S1 and T1 states.

A g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite has been successfully constructed. The structure and chemical composition of the composite were investigated via, inter alia, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The ability of the assembly to act as a photocatalyst for proton reduction to form hydrogen gas was studied. With visible light irradiation for 4 h, the total H2 production catalyzed by the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite was found to be 9 times as high as a corresponding CdSe/[Fe2S2(CO)6] assembly and significantly higher than either the CdSe quantum dots or g-C3N4 alone. The g-C3N4 support/matrix was found to enhance the stability and efficiency of the CdSe quantum dot/iron carbonyl cluster assembly in the photocatalytic hydrogen evolution process. Results from recycling tests showed that the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite is a sustainable and robust photocatalyst, maintaining the same activity after three cycles. The photoinduced charge carrier transfer dynamics in the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite system has been investigated by transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopies. The spectroscopic results indicate efficient hole transfer from the valence band of the excited CdSe quantum dots to the molecular iron carbonyl clusters and from the defect state of the quantum dots to g-C3N4 in the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite, which significantly inhibits the recombination of photogenerated charge carriers in CdSe quantum dots and boosts the photocatalytic activity and stability for hydrogen evolution. Energy transfer from g-C3N4 to the CdSe quantum dot/[Fe2S2(CO)6] assembly with a time constant of 0.7 ns also contributed to the charge transfer process.