Direct Photoexcitation Research Articles

Laser flash photolysis study of the photoinduced oxidation of 4-(dimethylamino)benzonitrile (DMABN).

Aromatic amines are aquatic contaminants for which phototransformation in surface waters can be induced by excited triplet states of dissolved organic matter (3DOM*). The first reaction step is assumed to consist of a one-electron oxidation process of the amine to produce its radical cation. In this paper, we present laser flash photolysis investigations aimed at characterizing the photoinduced, aqueous phase one-electron oxidation of 4-(dimethylamino)benzonitrile (DMABN) as a representative of this contaminant class. The production of the radical cation of DMABN (DMABN˙+) after direct photoexcitation of DMABN at 266 nm was confirmed in accord with previous experimental results. Moreover, DMABN˙+ was shown to be produced from the reactions of several excited triplet photosensitizers (carbonyl compounds) with DMABN. Second-order rate constants for the quenching of the excited triplet states by DMABN were determined to fall in the range of 3 × 107-5 × 109 M-1 s-1, and their variation was interpreted in terms of electron transfer theory using a Rehm-Weller relationship. The decay kinetics of DMABN˙+ in the presence of oxygen was dominated by a second-order component attributed to its reaction with the superoxide radical anion (O2˙-). The first-order rate constant for the transformation of DMABN˙+ leading to photodegradation of DMABN was estimated not to exceed ≈5 × 103 s-1.

Tuning the optical and electrical properties of MoS2 by selective Ag photo-reduction

Two-dimensional transition metal dichalcogenides have demonstrated potential for advanced electrical and optoelectronic applications. For these applications, it is necessary to modify their electrical or optoelectronic properties. Doping is one of the most prevalent techniques to modify the band structure of semiconductor materials. Herein, we report the p-type doping effect on few-layer and multi-layer MoS2 that are selectively decorated with Ag nanoparticles via laser-assisted direct photoexcitation of MoS2 exposed in AgNO3 solution. This method can control the doping level by varying the duration of the laser irradiation, which is confirmed by the observed gradual rise of MoS2 device channel resistance and photoluminescence spectra enhancement. This study demonstrated a simple, controllable, and selective doping technique using laser-assisted photo-reduction.

Time–frequency representation of autoionization dynamics in helium

Autoionization, which results from the interference between direct photoionization and photoexcitation to a discrete state decaying to the continuum by configuration interaction, is a well known example of the important role of electron correlation in light–matter interaction. Information on this process can be obtained by studying the spectral, or equivalently, temporal complex amplitude of the ionized electron wave packet. Using an energy-resolved interferometric technique, we measure the spectral amplitude and phase of autoionized wave packets emitted via the sp2+ and sp3+ resonances in helium. These measurements allow us to reconstruct the corresponding temporal profiles by Fourier transform. In addition, applying various time–frequency representations, we observe the build-up of the wave packets in the continuum, monitor the instantaneous frequencies emitted at any time and disentangle the dynamics of the direct and resonant ionization channels.

PH-dependent synthesis of iodine-deficient bismuth oxyiodide microstructures: Visible-light photocatalytic activity

Bismuth oxyiodides have exhibited high potential for applications in visible-light photocatalytic environmental remediation and solar energy conversion. In this work, a series of iodine-deficient bismuth oxyiodides (Bi4O5I2, Bi7O9I3, Bi5O7I) can be simply prepared through a pH-dependent aqueous procedure with feeding Bi/I ratio of 2:1. The compositions of the Bi-based oxyiodides are closely related to acid-base circumstances, with Bi4O5I2 formed in weakly acidic medium (pH = 5) and Bi7O9I3, Bi5O7I in basic medium (pH = 8 and 11). Morphology differences of nanosheet-assembled Bi4O5I2, Bi7O9I3 architectures and rod-like Bi5O7I microstructures demonstrate different crystalline characters and construction of Bi-based oxyiodide crystals. UV–vis DRS results revealed good visible-light absorptions of Bi4O5I2 and Bi7O9I3 architectures and appropriate band structures for photocatalytic reactions, on comparison to Bi5O7I microrods. Low electrochemical impedance of Bi7O9I3 microflowers with sheet-like units further facilitated the separation of e−–h+ carriers in the degradation process. Accordingly, among the bismuth oxyiodide samples, Bi7O9I3 displayed prominent visible-light degradation performance for colorless bisphenol-A (BPA) due to the direct photoexcitation process.

Exploring the Dynamics of the Photoinduced Ring-Opening of Heterocyclic Molecules.

Excited states formed by electron promotion to an antibonding σ* orbital are now recognized as key to understanding the photofragmentation dynamics of a broad range of heteroatom containing small molecules: alcohols, thiols, amines, and many of their aromatic analogues. Such excited states may be populated by direct photoexcitation, or indirectly by nonadiabatic transfer of population from some other optically excited state (e.g., a ππ* state). This Perspective explores the extent to which the fast-growing literature pertaining to such (n/π)σ*-state mediated bond fissions can inform and enhance our mechanistic understanding of photoinduced ring-opening in heterocyclic molecules.

Singlet Fission Reaction of Light-Exposed β-Carotene Bound to Bovine Serum Albumin. A Novel Mechanism in Protection of Light-Exposed Tissue by Dietary Carotenoids.

We have attempted to investigate the role of carotenoids (Car) in protecting pigment-protein complexes against light-induced degradation. Upon direct photoexcitation of β-carotene (β-Car), nanosecond flash photolysis and femtosecond time-resolved spectroscopy detected a substantial population of triplet states for β-Car aggregates associated with bovine serum albumin (BSA) or dispersed in aqueous phase with 10% tetrahydrofuran (THF), but none were observed for monomeric β-Car in neat THF. The direct photogeneration of triplet states was on the time scale of <1 ps, indicating that the underlying reaction mechanism was singlet fission (SF). Efficient triplet-triplet annihilation in the time regime from picoseconds to microseconds resulted in a <1 μs triplet lifetime for β-Car aggregates, in contrast to a 20 μs lifetime for monomeric β-Car as determined by anthracene-sensitized flash photolysis. The short-lived triplet excitations of β-Car aggregates associated with BSA or dispersed in aqueous phase were found to be insensitive to the presence of oxygen, which are considered to be important for the protection of both protein and carotenoid against light-induced degradation via reaction with oxidative species.

Mid-Infrared photorefractivity with non-degenerate two-photon absorption

Photorefractive grating recording with mid-infrared sub-picosecond light pulses (1.6 μm and longer wavelengths) might be possible in LiNbO3 crystals if the interaction area is illuminated additionally with pulses of visible light. Two processes can enable the experimentally observed MIR recording: One is related to the direct photoexcitation of a free electron via nonlinear absorption of two photons with different frequencies, one in the MIR and one in the visible range. The alternative possibility consists in an enhancement, caused by the diffraction of a visible pulse, of a very weak space-charge grating seeded solely by MIR radiation.

Structural, Morphological, Optical and Photocatalytic Properties of Y, N-Doped and Codoped TiO2 Thin Films

Pure TiO2, Y-N single-doped and codoped TiO2 powders and thin films deposited on glass beads were successfully prepared using dip-coating and sol-gel methods. The samples were analyzed using grazing angle X-ray diffraction (GXRD), Raman spectroscopy, time resolved luminescence, ground state diffuse reflectance absorption and scanning electron microscopy (SEM). According to the GXRD patterns and micro-Raman spectra, only the anatase form of TiO2 was made evident. Ground state diffuse reflectance absorption studies showed that doping with N or codoping with N and Y led to an increase of the band gap. Laser induced luminescence analysis revealed a decrease in the recombination rate of the photogenerated holes and electrons. The photocatalytic activity of supported catalysts, toward the degradation of toluidine, revealed a meaningful enhancement upon codoping samples at a level of 2% (atomic ratio). The photocatalytic activity of the material and its reactivity can be attributed to a reduced, but significant, direct photoexcitation of the semiconductor by the halogen lamp, together with a charge-transfer-complex mechanism, or with the formation of surface oxygen vacancies by the N dopant atoms.

Enhanced Solar-to-Hydrogen Generation with Broadband Epsilon-Near-Zero Nanostructured Photocatalysts.

The direct conversion of solar energy into fuels or feedstock is an attractive approach to address increasing demand of renewable energy sources. Photocatalytic systems relying on the direct photoexcitation of metals have been explored to this end, a strategy that exploits the decay of plasmonic resonances into hot carriers. An efficient hot carrier generation and collection requires, ideally, their generation to be enclosed within few tens of nanometers at the metal interface, but it is challenging to achieve this across the broadband solar spectrum. Here the authors demonstrate a new photocatalyst for hydrogen evolution based on metal epsilon-near-zero metamaterials. The authors have designed these to achieve broadband strong light confinement at the metal interface across the entire solar spectrum. Using electron energy loss spectroscopy, the authors prove that hot carriers are generated in a broadband fashion within 10 nm in this system. The resulting photocatalyst achieves a hydrogen production rate of 9.5 µmol h-1 cm-2 that exceeds, by a factor of 3.2, that of the best previously reported plasmonic-based photocatalysts for the dissociation of H2 with 50 h stable operation.

Enantioselective Formal α‐Methylation and α‐Benzylation of Aldehydes by Means of Photo‐organocatalysis

AbstractDetailed herein is the photochemical organocatalytic enantioselective α‐alkylation of aldehydes with (phenylsulfonyl)alkyl iodides. The chemistry relies on the direct photoexcitation of enamines to trigger the formation of reactive carbon‐centered radicals from iodosulfones, while the ground‐state chiral enamines provide effective stereochemical control over the radical trapping process. The phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl and benzyl groups.

Enantioselective Formal α-Methylation and α-Benzylation of Aldehydes by Means of Photo-organocatalysis.

Detailed herein is the photochemical organocatalytic enantioselective α‐alkylation of aldehydes with (phenylsulfonyl)alkyl iodides. The chemistry relies on the direct photoexcitation of enamines to trigger the formation of reactive carbon‐centered radicals from iodosulfones, while the ground‐state chiral enamines provide effective stereochemical control over the radical trapping process. The phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl and benzyl groups.

Is the Chemical Strategy for Imbuing "Polyene" Character in Diketopyrrolopyrrole-Based Chromophores Sufficient for Singlet Fission?

In this work, we have rationally designed and synthesized a novel thiophene-diketopyrrolopyrrole (TDPP)-vinyl-based dimer. We have investigated the optical and electronic properties and have probed the photophysical dynamics using transient absorption to investigate the possibility of singlet exciton fission. These revealed extremely rapid decay to the ground state (<50 ps), which we confirm is due to intramolecular excitonic processes rather than large-scale conformational change enabled by the vinyl linker. In all cases, the main excited state appears to be "dark", suggesting rapid internal conversion into a dark 2Ag-type singlet state. We found no evidence of triplet formation in TDPP-V-TDPP under direct photoexcitation. This may be a consequence of significant singlet stabilization in the dimer, bringing it below the energy needed to form two triplets. Our studies on this model compound set valuable lessons for design of novel triplet-forming materials and highlight the need for more broadly applicable design principles.

On a new mechanism of polariton–polariton scattering

Condensate states of a two-dimensional exciton–polariton system have been considered under the conditions of direct resonant photoexcitation. It has been theoretically predicted that splitting of eigenmodes with orthogonal polarizations leads to the emergence of a new channel of parametric scattering. A polariton condensate spontaneously decays into a set of states in a finite region of the momentum space, thus leading to a strong inhomogeneity in the distributions of the intensity and polarization even in the case of a strictly constant amplitude and zero in-plane momentum of the external field. The new scattering mechanism makes possible self-oscillating and chaotic states of polariton systems.

Electronic structure and dynamics of torsion-locked photoactive yellow protein chromophores.

The photocycle of photoactive yellow protein (PYP) begins with small-scale torsional motions of the chromophore leading to large-scale movements of the protein scaffold triggering a biological response. The role of single-bond torsional molecular motions of the chromophore in the initial steps of the PYP photocycle are not fully understood. Here, we employ anion photoelectron spectroscopy measurements and quantum chemistry calculations to investigate the electronic relaxation dynamics following photoexcitation of four model chromophores, para-coumaric acid, its methyl ester, and two analogues with aliphatic bridges hindering torsional motions around the single bonds adjacent to the alkene group. Following direct photoexcitation of S1 at 400 nm, we find that both single bond rotations play a role in steering the PYP chromophore through the S1/S0 conical intersection but that rotation around the single bond between the alkene moiety and the phenoxide group is particularly important. Following photoexcitation of higher lying electronic states in the range 346-310 nm, we find that rotation around the single bond between the alkene and phenoxide groups also plays a key role in the electronic relaxation from higher lying states to the S1 state. These results have potential applications in tuning the photoresponse of photoactive proteins and materials with chromophores based on PYP.

Influence of the nature of the anchoring group on electron injection processes at dye-titania interfaces.

We report (time-dependent) density functional theory calculations characterizing the changes in the electronic and optical properties of oligothiophene dyes when grafted on a titania surface via a carboxylic acid or catechol moiety as anchoring group, in relation to their use in dye-sensitized solar cells. The broadening of the LUMO level of the compounds upon adsorption has been extracted from the computed electronic structures and used to estimate electron injection times into the conduction band of the oxide. The strongly coupled carboxylic-containing dyes lead to faster electron injection times compared to catechol-substituted dyes. This difference is ascribed to the electron-donating character of the catechol moiety that polarizes the dye LUMO away from the dye@titania interface. The absorption spectra simulated at the TD-DFT level indicate that the grafted carboxylic-thiophene dyes undergo an indirect injection mechanism (type I) in which an intramolecular excitation is created before the charge is transferred to titania. In contrast, catechol dyes with a short conjugation length for the thiophene backbone are type II sensitizers exhibiting a direct injection mechanism leading to a direct photoexcitation from the dye HOMO to the titania conduction band. A mixed character prevails for the injection in the case of catechol dyes containing a longer oligothiophene chain.

Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation

Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot electrons generated from surface plasmon decay and from direct photoexcitation of the interband transitions of Al both contribute to this process. Our results pave the way for the use of aluminum, an earth-abundant, nonprecious metal, for photocatalysis.

Charge Separation and Recombination at Polymer-Fullerene Heterojunctions: Delocalization and Hybridization Effects.

We address charge separation and recombination in polymer/fullerene solar cells with a multiscale modeling built from accurate atomistic inputs and accounting for disorder, interface electrostatics and genuine quantum effects on equal footings. Our results show that bound localized charge transfer states at the interface coexist with a large majority of thermally accessible delocalized space-separated states that can be also reached by direct photoexcitation, thanks to their strong hybridization with singlet polymer excitons. These findings reconcile the recent experimental reports of ultrafast exciton separation ("hot" process) with the evidence that high quantum yields do not require excess electronic or vibrational energy ("cold" process), and show that delocalization, by shifting the density of charge transfer states toward larger effective electron-hole radii, may reduce energy losses through charge recombination.

Formation of a trithia[5]helicene in an unexpected photoreaction of a methyl-substituted bis(dithienylethenyl)thiophene through a double sequence of 6π-electrocyclization/aromatization (dehydrogenation/demethylation)

Abstract Photochemical reactions of 2,5-bis[2,2-di(thien-2-yl)ethenyl]thiophene (1a) and its tetramethyl derivative 1b, under direct photoexcitation, and photoinduced electron-transfer conditions, were studied. Our initial prediction was that 1b would undergo a photoreaction as part of a reversible photochromic system, while a reaction of its non-methyl substituted analog 1a would undergo a typical double sequence of 6π-electrocyclization (6π-EC)/aromatization (AR) (double dehydrogenation, 2H) to give 7,11-di(thien-2-yl)trithia[5]helicene (2a). In fact, we observed that photoirradiation of 1b leads to formation of the 7,11-bis(3-methylthien-2-yl)trithia[5]helicene (2b). In this process, 2b is formed via a double sequence of 6π-EC/AR (dehydrogenation/demethylation, H/ Me). Moreover, the yield of formation of 2b is much higher than that of 2a, which reacts through a double sequence of 6π-EC/AR ( 2H). Thus, this photochemically-induced paradoxical cascade reaction based on the newly uncovered reactivity serves as an efficient method to construct the trithia[5]helicene framework.

Direct and secondary nuclear excitation with x-ray free-electron lasers

The direct and secondary nuclear excitation produced by an x-ray free electron laser when interacting with a solid-state nuclear target is investigated theoretically. When driven at the resonance energy, the x-ray free electron laser can produce direct photoexcitation. However, the dominant process in that interaction is the photoelectric effect producing a cold and very dense plasma in which also secondary processes such as nuclear excitation by electron capture may occur. We develop a realistic theoretical model to quantify the temporal dynamics of the plasma and the magnitude of the secondary excitation therein. Numerical results show that depending on the nuclear transition energy and the temperature and charge states reached in the plasma, secondary nuclear excitation by electron capture may dominate the direct photoexcitation by several orders of magnitude, as it is the case for the 4.8 keV transition from the isomeric state of 93Mo, or it can be negligible, as it is the case for the 14.4 keV Mössbauer transition in 57Fe. These findings are most relevant for future nuclear quantum optics experiments at x-ray free electron laser facilities.

ChemInform Abstract: Enantioselective Organocatalytic Alkylation of Aldehydes and Enals Driven by the Direct Photoexcitation of Enamines.

AbstractThe asymmetric photo‐organocatalytic α‐ or γ‐alkylation of aliphatic aldehydes or α‐branched enals with bromomalonates, respectively, is described.