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Here we report gas-phase action and luminescence spectra of cationic dyes derived from oxazine: cresyl violet (CV⁺), oxazine 170 (Ox-170⁺), nile blue (NB⁺), darrow red (DR⁺), oxazine 1 (Ox-1⁺), oxazine 4 (Ox-4⁺), and brilliant cresyl blue (BCB⁺). The first four have a benzofused structure, which results in asymmetric charge distributions along the long axis. The positive charge is also asymmetrically distributed in BCB⁺ while Ox-1⁺ and Ox-4⁺ are symmetric. As the ions are isolated in vacuo, there are no interactions with solvent molecules or counter ions, and the effect of chemical modifications is therefore more easily revealed than from solution-phase experiments. The transition energy decreases in the order: DR⁺ > CV⁺ > Ox-4⁺ > Ox-170⁺ > BCB⁺ > Ox-1⁺ > NB⁺, and the fluorescence from BCB⁺ is less than from the others. We discuss the results based on electron delocalisation, degree of charge-transfer character, rigidity of the chromophore structure, and substituents.

Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH₂)_n. In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Förster Resonance Energy Transfer.

Photoacoustic (PA) imaging is an emerging medical imaging modality that combines optical excitation and ultrasound detection. Because ultrasound scatters much less than light in biological tissues, PA generates high-resolution images at centimeters depth. In recent years, wavelengths in the second near-infrared (NIR-II) window (1000 to 1700 nm) have been increasingly explored due to its potential for preclinical and clinical applications. In contrast to the conventional PA imaging in the visible (400 to 700 nm) and the first NIR-I (700 to 1000 nm) window, PA imaging in the NIR-II window offers numerous advantages, including high spatial resolution, deeper penetration depth, reduced optical absorption, and tissue scattering. Moreover, the second window allows a fivefold higher light excitation energy density compared to the visible window for enhancing the imaging depth significantly. We highlight the importance of the second window for PA imaging and discuss the various NIR-II PA imaging systems and contrast agents with strong absorption in the NIR-II spectral region. Numerous applications of NIR-II PA imaging, including whole-body animal imaging and human imaging, are also discussed.

Photoacoustic measurements are tested as a possible tool for non invasive quantification of Water/Collagen relative content in InterVertebral Discs (IVDs).

Electronic absorption spectra of water cluster anions (H₂O)_n^–, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid–vacuum interface.

GaN-based structures are promising for production of radiation detectors and high-voltage high-frequency devices. Particle detectors made of GaN are beneficial as devices simultaneously generating of the optical and electrical signals. Photon-electron coupling cross-section is a parameter which relates radiation absorption and emission characteristics. On the other hand, photon-electron coupling cross-section together with photo-ionization energy are fingerprints of deep centres in material. In this work, the wafer fragments of the GaN grown by ammonothermal (AT) technology are studied to reveal the dominant defects introduced by growth procedures and reactor neutron irradiations in a wide range, 10¹²–10¹⁶ cm⁻², of fluences. Several defects in the as-grown and irradiated material have been revealed by using the pulsed photo-ionization spectroscopy (PPIS) technique. The PPIS measurements were performed by combining femtosecond (40 fs) and nanosecond (4 ns) laser pulses emitted by optical parametric oscillators (OPO) to clarify the role of electron-phonon coupling. Variations of the operational characteristics of the tentative sensors, made of the AT GaN doped with Mg and Mn, under radiation damage by reactor neutrons have been considered.

Despite intense research into the optoelectronic properties of metal halide perovskites (MHPs), sub-bandgap absorption in MHPs remains largely unexplored. Here we recorded two-photon absorption spectra of MHPs using the time-resolved microwave conductivity technique. A two-step upward trend is observed in the two-photon absorption spectrum for methylammonium lead iodide, and some analogues, which implies that the commonly used scaling law is not applicable to MHPs. This aspect is further confirmed by temperature-dependent conductivity measurements. Using an empirical multiband tight binding model, spectra for methylammonium lead iodide were calculated by integration over the entire Brillouin zone, showing compelling similarity with experimental results. We conclude that the second upward trend in the two-photon absorption spectrum originates from additional optical transitions to the heavy and light electron bands formed by the strong spin-orbit coupling. Hence, valuable insight can be obtained in the opto-electronic properties of MHPs by sub-bandgap spectroscopy, complemented by modelling.

We used time-of-flight photocurrent measurements to determine the role of grain boundaries in charge carrier transport in thin layers of methyl ammonium lead iodide (CH₃NH₃PbI₃). The measurement results were compared to Kinetic Monte Carlo simulations, based on a transport model, which disentangles the transport within crystallites and hopping across grain boundaries. The observed mobilities of electrons are in the order ∼2.5 × 10⁻¹ cm²V⁻¹s⁻¹. The hopping across grains is modeled with an Arrhenius-type probability rate, characterized by activation energy (E_a). It was found that the E_a estimated from the slope of a mobility-temperature dependence is in the range of ∼56–70 meV. The factors contributing to E_a are shunting pathways and the grain-size variations including energy level misalignments at the grain boundaries. These results represent a step toward a design of novel windowless organic-inorganic perovskite solar cells.

Degradation of organic materials is responsible for the short operation lifetimes of organic light-emitting devices, but the mechanism by which such degradation is initiated has yet to be fully established. Here we report a new mechanism for degradation of emitting layers in blue-phosphorescent devices. We investigate binary mixtures of a wide bandgap host and a series of novel Ir(III) complex dopants having N-heterocyclocarbenic ligands. Our mechanistic study reveals the charge-neutral generation of polaron pairs (radical ion pairs) by electron transfer from the dopant to host excitons. Annihilation of the radical ion pair occurs by charge recombination, with such annihilation competing with bond scission. Device lifetime correlates linearly with the rate constant for the annihilation of the radical ion pair. Our findings demonstrate the importance of controlling exciton-induced electron transfer, and provide novel strategies to design materials for long-lifetime blue electrophosphorescence devices.

Nitrophenolates (NPs) are molecular anions that can undergo charge-transfer (CT) transitions determined by the degree of electron delocalization between the phenolate oxygen (donor group) and the nitro group (acceptor). Here we have studied four different NPs: 4’-nitro-[1,1’-biphenyl]-4-olate (1), 7-nitro-9H -carbazol-2-olate (NH linker, 2), 7-nitrodibenzo[b,d]furan-3-olate (oxygen linker, 3), and 7-nitrodibenzo[b,d]thiophen-3-olate (sulphur linker, 4), and recorded their electronic absorption spectra when isolated in vacuo to determine the effect of locking the biphenyl spacer group between
the donor and acceptor on transition energies. Absorption was identified from ion dissociation (action spectroscopy) using a homebuilt setup (sector mass spectrometer combined with pulsed laser). We find that the absorption is broad in the visible region for all four NPs with significant vibronic features. The lowest energy peak is at 601 ± 4 nm, 606 ± 4 nm, 615 ± 4 nm, and 620 ± 4 nm, for 3, 4, 2, and 1, respectively. NP 1 is flexible, and its lowest
energy structure is nonplanar while the other three NPs are planar according to density functional theory calculations. Hence in the case of 1 the electronic transition has a higher degree of CT than for the other three, accounting for its absorption furthest to the red. Our work demonstrates that oxygen and sulphur are best at conveying the electronic coupling between the donor and acceptor sites as 3 and 4 absorb furthest to the blue (i.e., the degree of CT is lowest for these two NPs). Based on the average spacing between the peaks in the vibrational progressions, coupling occurs to skeleton vibrational modes with frequencies of 649 ± 69 cm−1 (3), 655 ± 49 cm−1 (4), and 697 ± 52 cm−1 (2).