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At least 37 records · Page 2

Structural, Electronic, and Photophysical Insights into a Few Atom Copper-Sulfur Cluster in the Solid and Solution States

Coinage-metal chalcogenide clusters are widely studied for their attractive photoluminescence properties. Copper chalcogenides are especially promising, but are often confined to solid-state investigations due to their limited solution stability and the difficulty of synthesizing stable, well-defined clusters. Here, we investigate copper–sulfur clusters incorporating a small number of Cu atoms to elucidate fundamental atomic interactions, ground- and excited-state characteristics, and photophysical behavior in both solid and solution. We have synthesized the Cu6(4,6-dimethyl-2-mercaptopyrimidine)6 cluster in both neutral and charged states, Cu6 and Cu6-2H2+, respectively, by selective ligand protonation. The molecular structures are determined using single-crystal X-ray diffraction, while Cu K-edge X-ray absorption spectroscopy is used to probe Cu electronic structure differences arising from the ligand modification. Steady-state and pump-probe optical spectroscopy is used to investigate photophysical properties, interpreted using density functional theory methods. Both clusters exhibit good stability in the solid state and in solution and show characteristic near-infrared emission with microsecond lifetimes. Overall, the Cu6S6 clusters display favorable charge–transfer characteristics and show potential for further use in driving photochemical transformations.

Copper-sulfur clusters↗

Nanocrystal-to-Ligand Interfacial Thermal Transport: Plasmonic Indium Tin Oxide to Perylene Diimide Adsorbates

The generation and dissipation of heat in nanocrystals upon optical excitation is a process which may either limit or enhance their performance in certain applications. Using transient absorption spectroscopy, we tracked the flow of heat from plasmonic tin-doped indium oxide (ITO) nanocrystals to surface adsorbed perylenediimide (PDI) molecules upon excitation of the ITO near-infrared plasmon resonance. Here, we rationalize the derivative line shapes observed in the transient absorption bleach features are the result of thermal transfer from the ITO core to surface ligands based on temperature-dependent static absorption studies of the PDI molecules adsorbed on plasmonic ITO. Through a series of pump power dependent measurements, we demonstrate that the PDI heating time is largely fluence independent at the powers measured, while the overall recovery time increases. Elucidating thermal transfer rates at the nanocrystal and organic ligand interface is key for applications such as plasmon mediated photocatalysis, where heating may obfuscate hot carrier transfer processes.

heat dissipation↗

Investigating Np(VI) Nitrate Speciation Control through Temperature and Optical Spectroscopy

Numerous areas of nuclear processing, such as radioisotope production, nuclear waste remediation, and separations, depend upon the speciation of f-elements in the solution state. However, fundamental knowledge of the actinides─particularly Np─lags behind most of the elements on the periodic table. Despite the importance of Np(VI) chemistry in separations and nuclear processing, its speciation in HNO 3 remains uncertain. This work addresses some of these gaps by investigating the effect of HNO 3 concentration and temperature on the spectra and speciation of the Np(VI) nitrate system. Six samples of Np in 1 to 10 M HNO 3 were prepared and treated with (NH 4 ) 2 [Ce(NO 3 ) 6 ] to stabilize the hexavalent oxidation state. The absorbance spectrum of the 10 M HNO 3 is drastically different from the spectra of the other samples; the 10 M spectrum indicates coordination of nitrate ligands to the Np(VI)O 2 2+ ion to form a complex with high symmetry. Additionally, absorbance spectra were recorded over the temperature range of 15 to 40 °C, and systematic increases and decreases in certain spectral features of the ultraviolet–visible (UV–vis)–near-infrared (NIR) spectra are present in the spectra. The difference in spectral features suggests that Np(VI) nitrate speciation depends on temperature. Dilution studies of this sample were monitored with UV–vis–NIR and Raman spectroscopies. Spectral data indicate the presence of multiple complexes with different symmetries, including a high-symmetry complex with an inversion center. As samples are diluted and aquo ligands replace nitrate ligands bound to the Np(VI) neptunyl cation, changes in spectroscopic signals indicate a decrease in the high-symmetry nitrate complex and an increase in the lower-symmetry aquo complex. Additionally, the Raman band associated with the Np(VI)O 2 2+ symmetric stretch broadens with dilution and is fitted with two peaks. These peaks are assigned to Np(VI) aquo and nitrato complexes, indicating that this vibrational mode is sensitive to the coordination environment of the Np(VI) neptunyl cation and that contributions from these two Np(VI) complexes can be distinguished. This unique experimental data could be used to advance computational models describing the electronic transitions of complex actinyl ions.

Absorption↗

Self-supervised and multi-fidelity learning for extended predictive soil spectroscopy

Infrared spectroscopy is a cost-effective, non-destructive, and environmentally benign technology that is increasingly recognized as an important solution for meeting the global demand for soil data. While both near-infrared (NIR) and mid-infrared (MIR) diffuse reflectance spectroscopy enable rapid estimation of soil properties, they present a significant trade-off: NIR offers superior scalability and lower operational costs, whereas MIR provides higher analytical fidelity by capturing fundamental molecular vibrations. In this study, we propose a self-supervised, multi-fidelity learning framework designed to bridge this gap. Our approach leverages large-scale MIR spectral libraries to learn a compact, transferable latent representation, into which NIR spectra are subsequently aligned for downstream prediction. The workflow consists of pretraining a latent model on a large MIR library, adapting the representation using a smaller paired NIR–MIR dataset, and evaluating generalization on an independent external test set. Across a range of chemical and physical soil properties, we found that MIR-derived embeddings improved prediction accuracy relative to baseline models that used raw MIR inputs. Predictions derived from the spectrum conversion (NIR to MIR) task did not match the performance of the original MIR spectra but were similar or superior to predictive performance of NIR-only models, suggesting the unified spectral latent space can effectively leverage the larger and more diverse MIR dataset for prediction of soil properties not well represented in current NIR libraries.

54 ENVIRONMENTAL SCIENCES↗

Leveraging the redox activities of cerium and dibenzotetrathiafulvalene to discover a photo-responsive magnetic material

Stimuli-responsive changes in lanthanide-based materials are a promising research direction. In this study, [DBTTF] 4 [Ce 2 Cl 10 ] DBTTF = dibenzotetrathiafulvalene (1) was synthesized by a light-induced crystallization, where photo-oxidation of DBTTF enables formation of the cerium dimer [Ce 2 Cl 10 ] 4− . Intermolecular interactions between the stacked organic units of the crystal result in charge transfer bands in the visible-NIR (near-infrared) region, evident in the solid-state absorption spectrum upon comparison with the solution spectrum. The assignments of the sublattice oxidation states were made with single-crystal X-ray diffraction (SC-XRD) structural characterization, Raman spectroscopy, X-ray absorption spectroscopy, and magnetometry. Continuous 532 nm laser irradiation of the microcrystalline solid modulates the redox states in 1, leading to ∼40% reduction in the observed magnetization at 2 K. Density functional theory PBE+U/HSE06 band structure calculations predict Mott insulating behavior in 1, with a bandgap of 0.54/0.81 eV, and further support the conjecture that the observed photo-induced change in magnetization results from electron transfer from the [Ce 2 Cl 10 ] 4− anions to the π-stacked [DBTTF] 2 2+ organic dimer subunits. An enhancement in conductivity is similarly observed upon 532 nm irradiation, determined by single-crystal transport measurements. The findings reveal that photo-responsive lanthanide-based materials can be achieved by integration of redox-active organic moieties with redox-active lanthanide cations for the realization of switchable, photo-magnetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Attosecond control and measurement of chiral photoionization dynamics

Many chirality-sensitive light–matter interactions are governed by chiral electron dynamics. Therefore, the development of advanced technologies making use of chiral phenomena would critically benefit from measuring and controlling chiral electron dynamics on their natural attosecond timescales. Such endeavours have so far been hampered by the lack of characterized circularly polarized attosecond pulses, an obstacle that has recently been overcome. Here we introduce chiroptical spectroscopy with attosecond pulses and demonstrate attosecond coherent control over photoelectron circular dichroism (PECD), as well as the measurement of chiral asymmetries in the forward–backward and angle-resolved photoionization delays of chiral molecules. We show that co-rotating attosecond and near-infrared (IR) pulses can nearly double the PECD and even change its sign compared with single-photon ionization. We demonstrate that chiral photoionization delays depend on both polar and azimuthal angles of photoemission in the light-propagation frame, requiring 3D momentum resolution. We measure forward–backward chiral-sensitive delays of up to 60 as and polar-angle-resolved photoionization delays of up to 240 as, which include an asymmetry of about 60 as originating from chirality in the continuum–continuum transitions. Attosecond chiroptical spectroscopy opens the door to quantitatively understanding and controlling the dynamics of chiral molecules on the electronic timescale.

Atomic and molecular interactions with photons↗

Highly Conjugated Porphyrin Arrays Enable Optical Resolution of Ferromagnetic and Antiferromagnetic Aligned States of the Triplet Exciton and an Incorporated Stable Radical

Well-defined photogenerated molecular spin systems have potential utility in spintronics and quantum information science (QIS). Because molecular magnetic, optical, and electronic properties can be controlled by design, diverse spin systems can be prepared at modest temperatures. Photogenerated molecular spin systems often involve states prepared from the interaction of excitons and charges. Resolving the nature of electron spin alignment in photogenerated spin states described by the coupling of a triplet exciton and a stable radical commonly relies on EPR spectroscopy. Here, we describe ethyne-bridged (porphinato)metal ( PM n ) oligomers that incorporate a macrocycle-bound Cu(II) radical center. Upon photoexcitation of such PM n arrays, a singdoublet ( 2 S 1 ) state is formed; ultrafast internal conversion (IC) then produces a tripdoublet ( 2 T 1 ) state, which undergoes intersystem crossing (ISC) to produce a tripquartet ( 4 T 1 ) state, before relaxation to the ground state ( 2 S 0 ). These highly conjugated Cu(II) radical-containing PMn arrays enable direct observation of copper porphyrin 2 T 1 → 4 T 1 ISC dynamics from the biexponential decay of the near-infrared (NIR) 2,4 T 1 → 2,4 T n transient absorption manifold. Multireference n-electron valence perturbation theory (NEVPT2) computations illuminate how PM n electronic structure controls the relaxation dynamics of these long-lived (>10 ns) electronically excited multiplet states. These studies show that highly conjugated and polarizable porphyrin arrays incorporating stable spin centers provide rare π-delocalized systems where the ferromagnetic and antiferromagnetic alignment between a triplet exciton and a stable radical are both spectrally resolved and addressable using transient optical spectroscopy at wavelengths exceeding 1 μm, providing new opportunities to QIS.

14 SOLAR ENERGY↗

Attosecond Optical Orientation

Circularly polarized light offers opportunities to probe symmetry-dependent properties of matter such as chirality and spin. Circular-dichroic measurements typically require further intrinsic or extrinsic breaking of symmetry by, e.g., enantiomeric excess, orientation, magnetic fields, or direction-sensitive detectors. Here we introduce circular-dichroic attosecond transient absorption spectroscopy by leveraging the angular momentum of two circularly polarized pulses, both pump and probe, in an isotropic medium, optically orienting the angular momentum of excited states on an attosecond timescale. We investigate a circular-dichroic measurement of the attosecond transient absorption of He Rydberg states. By limiting the allowed pathways via dipole selection rules for co- and counterrotating circularly polarized near-infrared and extreme ultraviolet (XUV) pulses, different spectral reshapings of the XUV transient absorption due to the AC Stark effect are observed. Furthermore, paired with time-dependent Schrödinger equation calculations, the results show the role of selection and propensity rules and open up new opportunities to study coupling pathways of excited states as well as spin-dependent dynamics in atoms and beyond via attosecond optical orientation.

Angular momentum of light↗

Heterovalent Substitution of K 2 SrP 2 O 7 :Cr 3+ to Achieve Anti-Thermal-Quenching Broadband Near-Infrared Luminescence

Broadband near-infrared (NIR) light sources based on phosphor-converted light-emitting diodes are highly desirable for biochemical analysis and medical diagnosis applications. However, thermal quenching remains a demanding challenge for developing efficient NIR phosphors. Herein, we report the enhancement of both quantum efficiency and thermal stability in Cr 3+ -activated K 2 SrP 2 O 7 phosphors through a heterovalent substitution strategy by replacing Sr 2+ with Al 3+ in K 2 Sr 1–x Al x P 2 O 7 (0.05 ≤ x ≤ 0.2) to obtain optimized broadband NIR emission. Structural modulation via Al 3+ substitution leads to the optimized composition, K 2 Sr 0.88 Al 0.1 P 2 O 7 :0.02Cr 3+ , which emits across a broad NIR range of 650–1100 nm peaking at 807 nm with a full width at half-maximum of ∼130 nm under 448 nm excitation. Remarkably, its emission intensity at 150 °C remains 120% of the initial value at room temperature, demonstrating a rare antithermal-quenching behavior. Temperature-dependent XRD studies further reveal that Al 3+ substitution effectively suppresses lattice expansion at elevated temperatures, indicating enhanced lattice stability under thermal excitation. Detailed structural and spectral analyses show that the substitution enhances local site symmetry, reduces electron–phonon coupling, increases thermally induced absorption probability, and fortifies energetic barriers against nonradiative transitions. These synergistic effects collectively endow this NIR phosphor with a superior thermal stability. Furthermore, NIR light-emitting diodes fabricated with this phosphor exhibit strong potential for applications in information identification, nondestructive detection, and night vision technologies. This study demonstrates a local structure engineering strategy for designing thermally robust Cr 3+ -activated NIR phosphors, offering valuable insights into material discovery and NIR spectroscopy device development.

Cr3+↗

Fiber-Coupled Multipass NIR Sensor for In Situ, Real-Time Water Vapor Outgassing Monitoring

This work presents the recent development of a fiber-coupled multipass near-infrared (NIR) gas sensor used to monitor water vapor desorption of small material coupons. The gas sensor design employs a White cell topology to maximize the optical path length over a compact, hand-size footprint. Water vapor concentrations are quantified over a large dynamic range by simultaneously applying wavelength modulation and tunable diode laser absorption spectroscopy techniques. A custom headspace optimized for material desorption experiments is assembled using commercially available vacuum chamber components. We provide in situ measurements of water vapor desorption from two geometries of the industrially important silicone elastomer Sylgard-184 as a case study for sensor viability. To corroborate the results, the gas sensor data are compared to numerical simulations based on a triple-mode diffusion–sorption model, consisting of Henry, Langmuir, and Pooling modes.

gas sensor↗

Probing Surface Plasmon Dynamics in Periodic Nanostructures through Ultrafast Electron Microscopy

Surface plasmon polaritons (SPPs) can be manipulated to localize and guide light in subwavelength distances, enabling them to find applications in a wide range of areas, from sensing to quantum computing. Among several methods of SPP excitation, periodic arrays of nano- and microstructures are of particular interest, as they enable engineering SPP properties through structural parameters. Here, in this study, using the photon-induced near-field electron microscopy (PINEM) technique, we investigated the mode formation, coupling, interference, and decay of SPPs in square and hexagonal arrays of circular nanoholes under both visible and near-infrared excitation. Polarization-resolved analysis revealed the key factors governing SPP localization and interference patterns, showing that the periodicity and symmetry of the array primarily determine the SPP interference patterns and their orientation, while pump polarization mainly modulates their intensity. Time-resolved PINEM measurements demonstrated the spatial dependence of the SPP temporal characteristics. In addition, cathodoluminescence (CL) spectroscopy was employed to examine the intrinsic plasmonic characteristics of the structure. Finite difference time domain (FDTD) simulations showed strong agreement with both PINEM and CL measurements on the spatial and spectral behavior of SPPs. Understanding the spatiotemporal dynamics of SPPs on nanostructures beyond the diffraction limit is crucial for optimizing plasmonic structures for advanced photonic and quantum technologies.

Plasmonics↗

Correlation of optical properties with particle size, morphology, and polymorph of fine- and nano-particle formulations of titanium dioxide powders

Titanium dioxide (TiO 2 ) particulates are known to exhibit different visible and infrared optical properties compared to the bulk material, showing strong dependence on particle size, crystal structure, and morphology. In this study, the optical properties, sizes, and morphologies of TiO 2 particles from two different sources (nano and fine powders) having a) nominally different particle sizes and b) various crystal polymorph mixture fractions are compared using a combination of single particle mass spectrometry, optical spectroscopies, and aerosol characterization methods. The nano sample was found to be largely particles of the anatase polymorph (88% by mass), while the fine sample was found to consist largely of rutile particles (95% by mass). Two distinct particle morphologies (fractal and compact) were found in each powder sample and could be identified and separated in-situ based on particle aerodynamic properties. The attenuation of near-infrared, visible and ultraviolet light by TiO 2 particles shows strong dependence on particle morphology. Furthermore, while the fine particles were found to have larger near-infrared (675–800 nm) extinction coefficients by mass than the nanoparticles, the reverse was true in the ultraviolet and visible regions (370–675 nm). However, for polydisperse particles with different sizes and shapes, the optical behaviors are not straightforward to directly correlate to a combination of physical parameters.

Lockwood, Schuyler P. [Pacific Northwest National ↗

Tuning Anisotropic Optical Properties of Inorganic and Hybrid Organic–Inorganic MXenes via Topochemical Surface Modification

Surface groups are central to the properties of MXenes, yet their role in optical anisotropy remains largely unexplored. Here, we use a topochemical route to synthesize single crystals of stacked Ti 3 C 2 Cl 2 and hybrid organic–inorganic MXenes (h-MXenes) with lateral sizes of 38–75 μm, rotational registry, and tunable interlayer spacing. Solid-state NMR spectroscopy shows that topochemical substitution generates mixed amido, imido, and hydride surface motifs, which modify the electronic structure of the Ti 3 C 2 inorganic core. Imaging spectroscopic ellipsometry with micron-scale spatial resolution enables reconstruction of the complex dielectric tensor of individual multilayer crystals. Ti 3 C 2 Cl 2 exhibits a type-II hyperbolicity above 930 nm, whereas h-MXenes do not display hyperbolicity within the measured 300–1700 nm window, instead showing reduced in-plane conductivity, suppressed out-of-plane light absorption, and a chain-length-dependent blue shift of a near-infrared absorption feature. These results demonstrate topochemical surface modification as a direct handle for engineering MXenes as surface-programmable optical media.

Hybrid materials↗

Anisotropic strain relaxation-induced directional ultrafast carrier dynamics in RuO 2 films

Ultrafast light-matter interactions inspire potential functionalities in picosecond optoelectronic applications. However, achieving directional carrier dynamics in metals remains challenging due to strong carrier scattering within a multiband environment, typically expected for isotropic carrier relaxation. In this study, we demonstrate epitaxial RuO 2 /TiO 2 (110) heterostructures grown by hybrid molecular beam epitaxy to engineer polarization selectivity of ultrafast light-matter interactions via anisotropic strain engineering. Combining spectroscopic ellipsometry, x-ray absorption spectroscopy, and optical pump-probe spectroscopy, we revealed the strong anisotropic transient optoelectronic response at an excitation energy of 1.58 eV in strain-engineered RuO 2 /TiO 2 (110) heterostructures along both in-plane [001] and [1$\bar1$0] crystallographic directions. Theoretical analysis identifies strain-induced modifications in band nesting as the underlying mechanism for enhanced anisotropic carrier relaxation observed at this excitation energy. These findings establish epitaxial strain engineering as a powerful tool for tuning anisotropic optoelectronic responses with near-infrared excitations in metallic systems, paving the way for next-generation polarization-sensitive ultrafast optoelectronic devices.

Science & Technology - Other Topics↗

Near-Infrared Photoluminescence from Spin-Flip Excited States of π-Conjugated Tris(quinolinolate) Chromium(III) Complexes

Tuning metal–ligand covalency offers promising design strategies to tailor the photoluminescence (PL) emission energies of metal-centered, spin-flip excited states. Herein, we report a series of tris(quinolinolate) chromium(III) complexes that exhibit record-low near-infrared II emission energies in a fluid solution at room temperature, afforded by their strong metal–ligand covalencies. Appending π-conjugated arylethynyl substituents to quinolinolate ligands resulted in minimal changes to metal–ligand bond lengths, facilitating nearly indiscriminate metal–ligand covalencies for each tris(quinolinolate) chromium(III) complex. As a result, near-infrared II emission was observed across the series, while simultaneously affording careful tuning of the 4 LMCT/ 4 ( 1 ILCT) electronic transition energies across the visible region. Here, detailed analyses of ground-state electronic structures and excited-state electronic transitions revealed that PL arises from a ligand-field, 2 E excited state, admixed with charge-transfer character. This assignment was supported by solvent-dependent near-infrared emission energies and long excited-state lifetimes, consistent with spin-forbidden relaxation (ranging from 115 ± 5 to 123 ± 1 ns across the series). Utilizing spectroscopic data, ligand-field parameters were quantified, further rationalizing the role of strong metal–ligand covalency in enabling near-infrared II emission. Supported by these results, this study presents a new class of ligands that enable room-temperature near-infrared II emission in chromium(III)-based spin-flip excited states.

Absorption spectroscopy↗

Au 76 (SC 6 H 4 - p -CH 3 ) 42 Square Quantum Platelet: One-Dimensional Growth of Quantum Rods Turns 90 Degrees

The growth pattern of atomically precise nanoclusters (NCs) is of fundamental interest, and the structural effect on their photoluminescence (PL) is important owing to their PL in the second near-infrared (NIR-II) range (900–1700 nm optoelectronically or 1000–1700 nm biologically) that holds great promise for optoelectronic and biomedical applications. Because of the small energy gaps required for NIR-II emission, the PL performance of NIR-II luminophores is largely limited by nonradiative processes. In this work, we discovered a Au 76 (p-MBT) 42 (Au 76 ) (p-MBTH = p-methylbenzenethiol) nanocluster featuring a face-centered cubic (fcc) core in a square shape (edge length: 1 nm). This square quantum platelet can be viewed as a side-facet (010) growth of the Au 52 (p-MBT) 32 (Au 52 ) rod, as opposed to the (001) facet growth. We found that Au 76 exhibits bright emission centered at 970 nm with a PL quantum yield (PLQY) of 30% in solution under ambient conditions, which can be further enhanced to 40% when the solution is deaerated. X-ray crystallography analysis coupled with time-resolved spectroscopy revealed that the nearly doubled PLQY compared to Au 52 (18.3%) was resulted from shorter Au–Au bond lengths in Au 76 (average 2.835 Å) than that in Au 52 (3.04 Å). This work provides important insights into the design of highly luminescent NCs, which are promising for photovoltaics, photocatalysis, and optoelectronic applications.

36 MATERIALS SCIENCE↗

Imaging transient molecular configurations in UV-excited diiodomethane

Femtosecond structural dynamics of diiodomethane (CH 2 I 2 ) triggered by ultraviolet (UV) photoabsorption at 290 and 330 nm are studied using time-resolved coincident Coulomb explosion imaging driven by a near-infrared probe pulse. Here, we map the dominant single-photon process, the cleavage of the carbon–iodine bond producing rotationally excited CH 2 I radical, identify the contributions of the three-body (CH 2 + I + I) dissociation and molecular iodine formation channels, which are primarily driven by the absorption of more than one UV photon, and demonstrate the existence of a weak reaction pathway involving the formation of short-lived transient species resembling iso-CH 2 I 2 -like geometries with a slightly shorter I–I separation compared to the ground-state CH 2 I 2 . These transient molecular configurations, which can be separated from the other channels by applying a set of conditions on the correlated momenta of three ionic fragments, are formed within ∼100 fs after the initial photoexcitation and decay within the next 100 fs.

Atomic and molecular processes↗

Above the Energy Gap Law: Heavy Chalcogenide Substitution in NIR II-Emissive Diradicaloid Qubits

Near-infrared (NIR, 700–1700 nm)- and telecom (∼1260–1625 nm)-emissive molecules are good candidates for biological imaging and quantum sensing applications, respectively; however, bright low energy emission is rare due to exponentially increasing nonradiative decay rates in these regions, a phenomenon known as the energy gap law. Recent literature has emphasized the importance of minimizing skeletal modes to prevent increased nonradiative decay rates, but most organic lumiphores in these regions utilize large, conjugated scaffolds containing many C═C modes. Here we report a compact, telecom-emissive scaffold, tetrathiafulvalene-2,3,6,7-tetraselenate, or TTFts, that displays remarkable air, water, and acid stability, exhibits record quantum yields and brightness values, and retains quantum coherence under ambient conditions. These properties are enabled through methodical selenium substitution, which bathochromically shifts emission while shifting skeletal vibrations to lower energies. This new scaffold validates heavy heteroatom substitution strategies and establishes a new class of bright telecom emitters and robust qubits.

biological imaging↗