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Background: Paricalcitol, a vitamin D analog, is commonly administered three times weekly to control secondary hyper parathyroidism in hemodialysis patients. Less frequent dosing would be more convenient, require less nursing time, and be an option in other dialysis modalities. No studies have examined the efficacy of once-weekly dosing of paricalcitol. Methods: Chronic hemodialysis patients receiving a stable dose of paricalcitol three times weekly with intact PTH (iPTH) 100-500 ng/l were monitored during a two-week base line, then were converted to a single mid-week paricalcitol dose equal to the previous cumulative weekly dose. Serum calcium and phosphorus were monitored weekly and iPTH levels determined during study Weeks 4 and 8. A single paricalcitol dose adjustment was made during study Week 5 based on iPTH to achieve a target value of 150-300 ng/l. Phosphate binders and calcium dialysate bath were kept constant during the study. Results: In the 25 patients, mean iPTH was 295 ± 107 ng/l at base line, and not significantly different at Week 4 (307 ± 111 ng/l) or Week 8 (285 ± 98 ng/l). Paricalcitol dose in creases mid-study were almost exclusively in patients with iPTH > 300 ng/l. Calcium, phosphorus, and calcium × phosphorus product were not significantly different on weekly therapy. (Only one patient developed a calcium > 2.55 mmol/l during the study.) Conclusion: Once-weekly dosing of paricalcitol is an effective option in treatment of secondary hyperparathyroidism. Less frequent dosing may better allocate nursing time and potentially benefit other patient populations with CKD and ESRD. [ABSTRACT FROM AUTHOR]

The analysis of methol in encapsulated products is challenging due tothe nature of the encapsulating matrices and the volatility of the analyte. Normal sampling/extraction procedures cannot be applied to the different types of menthol encapsulated products, due to variable extraction efficiencies of the analyte. This paper details the extraction and analysis of menthol flavour using a two stage thermal desorption GC process. This two stage thermal desorption system, using a Tenax TR packed cold trap, enables a narrow band of the extracted menthol to be focused onto the GC column. The method showed linearity in the range of 0.2-0.8mg of menthol with a correlation coefficient greater than 0.999. Average instrumental precision of 3% RSD was determined and method precision was in the range of 2.1-9.4% RSD. This method was specific tomenthol showing no interfering peaks. All the menthol was extracted in one extraction step. The specific analysis of menthol in encapsulated products allowed comparison of the efficiency of encapsulating processes, by comparing menthol loading values. RSD values for the different microparticles also indicate the relative homogeneity of the systems. [ABSTRACT FROM AUTHOR]

Indoramin hydrochloride lowered blood pressure to a significantly greater and more prolonged extent than propranolol. It induced bradycardia and reduced peak left ventricular dp/dt, concomitant with a decrease in peripheral resistance. Propranolol reflexly increased peripheral resistance, thus accounting for the transient nature of its vasodepressor action. The sustained nature of the hypotensive action of indoramin was related to its α-adrenoceptor blocking property in the periphery. The cardiovascular actions of indoramin also differed from those of lignocaine and quinidine. [ABSTRACT FROM PUBLISHER]

Thiomaleimides undergo efficient intermolecular [2 + 2] photocycloaddition reactions and offer applications from photochemical peptide stapling to polymer crosslinking; however, the reactions are limited to the formation of the exo head-to-head isomers. Herein, we present an intramolecular variation which completely reverses the stereochemical outcome of this photoreaction, quantitatively generating endo adducts which minimise the structural disturbance of the disulfide staple and afford a 10-fold increase in quantum yield. We demonstrate the application of this reaction on a protein scaffold, using light to confer thiol stability to an antibody fragment conjugate. To understand more about this intriguing class of [2 + 2] photocycloadditions, we have used transient absorption spectroscopy (electronic and vibrational) to study the excited states involved. The initially formed S 2 (π 1 π*) excited state is observed to decay to the S 1 (n 1 π*) state before intersystem crossing to a triplet state. An accelerated intramolecular C-C bond formation provides evidence to explain the increased efficiency of the reaction, and the impact of the various excited states on the carbonyl vibrational modes is discussed., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

Many photoactivated processes involve a change in oxidation state during the reaction pathway and formation of highly reactive photoactivated species. Isolating these reactive species and studying their early-stage femtosecond to nanosecond (fs-ns) photodynamics can be challenging. Here we introduce a combined ultrafast transient absorption-spectroelectrochemistry (TA-SEC) approach using freestanding boron doped diamond (BDD) mesh electrodes, which also extends the time domain of conventional spectrochemical measurements. The BDD electrodes offer a wide solvent window, low background currents, and a tuneable mesh size which minimises light scattering from the electrode itself. Importantly, reactive intermediates are generated electrochemically, via oxidation/reduction of the starting stable species, enabling their dynamic interrogation using ultrafast TA-SEC, through which the early stages of the photoinduced relaxation mechanisms are elucidated. As a model system, we investigate the ultrafast spectroscopy of both anthraquinone-2-sulfonate (AQS) and its less stable counterpart, anthrahydroquinone-2-sulfonate (AH 2 QS). This is achieved by generating AH 2 QS in situ from AQS via electrochemical means, whilst simultaneously probing the associated early-stage photoinduced dynamical processes. Using this approach we unravel the relaxation mechanisms occurring in the first 2.5 ns, following absorption of ultraviolet radiation; for AQS as an extension to previous studies, and for the first time for AH 2 QS. AQS relaxation occurs via formation of triplet states, with some of these states interacting with the buffered solution to form a transient species within approximately 600 ps. In contrast, all AH 2 QS undergoes excited-state single proton transfer with the buffered solution, resulting in formation of ground state AHQS - within approximately 150 ps., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Artificial light-harvesting systems in aqueous media which mimic nature are of significant importance; however, they are often restrained by the solubility and the undesired aggregation-caused quenching effect of the hydrophobic chromophores. Here, we report a generalized strategy toward the construction of efficient artificial light-harvesting systems based on supramolecular peptide nanotubes in water. By molecularly aligning the hydrophobic chromophores along the nanotubes in a slipped manner, an artificial light-harvesting system with a two-step sequential Förster resonance energy transfer process is successfully fabricated, showing an energy transfer efficiency up to 95% and a remarkably high fluorescence quantum yield of 30%, along with high stability. Furthermore, the spectral emission could be continuously tuned from blue through green to orange, as well as outputted as a white light continuum with a fluorescence quantum yield of 29.9%. Our findings provide a versatile approach of designing efficient artificial light-harvesting systems and constructing highly emissive organic materials in aqueous media.

Sinapoyl malate is a natural plant sunscreen molecule which protects leaves from harmful ultraviolet radiation. Here, the ultrafast dynamics of three sinapoyl malate derivatives, sinapoyl L-dimethyl malate, sinapoyl L-diethyl malate and sinapoyl L-di-t-butyl malate, have been studied using transient electronic absorption spectroscopy, in a dioxane and methanol solvent environment to investigate how well preserved these dynamics remain with increasing molecular complexity. In all cases it was found that, upon photoexcitation, deactivation occurs via a trans-cis isomerisation pathway within ∼20-30 ps. This cis-photoproduct, formed during photodeactivation, is stable and longed-lived for all molecules in both solvents. The incredible levels of conservation of the isomerisation pathway with increased molecular complexity demonstrate the efficacy of these molecules as ultraviolet photoprotectors, even in strongly perturbing solvents. As such, we suggest these molecules might be well-suited for augmentations to further improve their photoprotective efficacy or chemical compatibility with other components of sunscreen mixtures, whilst conserving their underlying photodynamic properties., (© 2020 Wiley-VCH GmbH.)

Atomic-scale defects can control the exploitable optoelectronic performance of crystalline materials, and several point defects in diamond are emerging functional components for a range of quantum technologies. Nitrogen and hydrogen are common impurities incorporated into diamond, and there is a family of defects that includes both. The N 3 VH 0 defect is a lattice vacancy where three nearest neighbor carbon atoms are replaced with nitrogen atoms and a hydrogen is bonded to the remaining carbon. It is regularly observed in natural and high-temperature annealed synthetic diamond and gives rise to prominent absorption features in the mid-infrared. Here, we combine time- and spectrally resolved infrared absorption spectroscopy to yield unprecedented insight into the N 3 VH 0 defect's vibrational dynamics following infrared excitation of the C-H stretch. In doing so, we gain fundamental information about the energies of quantized vibrational states and corroborate our results with theory. We map out, for the first time, energy relaxation pathways, which include multiphonon relaxation processes and anharmonic coupling to the C-H bend mode. These advances provide new routes to quantify and probe atomic-scale defects.

Ferroelectric-paraelectric superlattices show emerging new states, such as polar vortices, through the interplay and different energy scales of various thermodynamic constraints. By introducing magnetic coupling at BiFeO 3 -La 0.7 Sr 0.3 MnO 3 interfaces epitaxially grown on SrTiO 3 substrate, we find, for the first time in thin films, a sub-nanometer thick lamella-like BiFeO 3 . The emergent phase is characterized by an arrangement of a two unit cell thick lamella-like structure featuring antiparallel polarization, resulting an antiferroelectric-like structure typically associated with a morphotropic phase transition. The antipolar phase is embedded within a nominal R 3 c structure and is independent of the BiFeO 3 thickness (4-30 unit cells). Moreover, the superlattice structure with the morphotropic phase demonstrates azimuth-independent second harmonic generation responses, indicating a change of overall symmetry mediated by a delicate spatial distribution of the emergent phase. This work enriches the understanding of a metastable state manipulated by thermodynamic constraints by lattice strain and magnetic coupling.

Heterostructures built from 2D, atomically thin crystals are bound by the van der Waals force and exhibit unique optoelectronic properties. Here, we report the structure, composition and optoelectronic properties of 1D van der Waals heterostructures comprising carbon nanotubes wrapped by atomically thin nanotubes of boron nitride and molybdenum disulfide (MoS 2 ). The high quality of the composite was directly made evident on the atomic scale by transmission electron microscopy, and on the macroscopic scale by a study of the heterostructure's equilibrium and ultrafast optoelectronics. Ultrafast pump-probe spectroscopy across the visible and terahertz frequency ranges identified that, in the MoS 2 nanotubes, excitons coexisted with a prominent population of free charges. The electron mobility was comparable to that found in high-quality atomically thin crystals. The high mobility of the MoS 2 nanotubes highlights the potential of 1D van der Waals heterostructures for nanoscale optoelectronic devices.

Hypoxic tumours are a major problem for cancer photodynamic therapy. Here, we show that photoredox catalysis can provide an oxygen-independent mechanism of action to combat this problem. We have designed a highly oxidative Ir(III) photocatalyst, [Ir(ttpy)(pq)Cl]PF 6 ([1]PF 6 , where 'ttpy' represents 4'-(p-tolyl)-2,2':6',2''-terpyridine and 'pq' represents 3-phenylisoquinoline), which is phototoxic towards both normoxic and hypoxic cancer cells. Complex 1 photocatalytically oxidizes 1,4-dihydronicotinamide adenine dinucleotide (NADH)-an important coenzyme in living cells-generating NAD • radicals with a high turnover frequency in biological media. Moreover, complex 1 and NADH synergistically photoreduce cytochrome c under hypoxia. Density functional theory calculations reveal π stacking in adducts of complex 1 and NADH, facilitating photoinduced single-electron transfer. In cancer cells, complex 1 localizes in mitochondria and disrupts electron transport via NADH photocatalysis. On light irradiation, complex 1 induces NADH depletion, intracellular redox imbalance and immunogenic apoptotic cancer cell death. This photocatalytic redox imbalance strategy offers a new approach for efficient cancer phototherapy.

Materials with electrically tunable optical properties offer a wide range of opportunities for photonic applications. The optical properties of the single-walled carbon nanotubes (SWCNTs) can be significantly altered in the near-infrared region by means of electrochemical doping. The states' filling, which is responsible for the optical absorption suppression under doping, also alters the nonlinear optical response of the material. Here, for the first time we report that the electrochemical doping can tailor the nonlinear optical absorption of SWCNT films and demonstrate its application to control pulsed fiber laser generation. With a pump-probe technique, we show that under an applied voltage below 2 V the photobleaching of the material can be gradually reduced and even turned to photoinduced absorption. Furthermore, we integrated a carbon nanotube electrochemical cell on a side-polished fiber to tune the absorption saturation and implemented it into the fully polarization-maintaining fiber laser. We show that the pulse generation regime can be reversibly switched between femtosecond mode-locking and microsecond Q-switching using different gate voltages. This approach paves the road toward carbon nanotube optical devices with tunable nonlinearity.

Photoprotection from harmful ultraviolet (UV) radiation exposure is a key problem in modern society. Mycosporine-like amino acids found in fungi, cyanobacteria, macroalgae, phytoplankton, and animals are already presenting a promising form of natural photoprotection in sunscreen formulations. Using time-resolved transient electronic absorption spectroscopy and guided by complementary ab initio calculations, we help to unravel how the core structures of these molecules perform under UV irradiation. Through such detailed insight into the relaxation mechanisms of these ubiquitous molecules, we hope to inspire new thinking in developing next-generation photoprotective molecules.

Continuous advancements in biophysics and medicine at the molecular level make the requirements to image structure-function processes in living cells ever more acute. While fluorophores such as the green fluorescent protein have proven instrumental toward such efforts, the advent of nondiffraction limited microscopy limits the utility of such fluorescent tags. Monoaminomaleimides are small, single molecule fluorophores that have been shown to possess stark variations in their emission spectra in different solvent environments, making them a potentially powerful tool for a myriad of applications. The ability to "autotune" fluorescence according to different media allows for a probe capable of working in all regions of a cell, or accurately characterizing the purity of an environment. In this work, we present ultrafast pump-probe studies of a model monoaminomaleimide, 1-methyl-3-(methylamino)-1H-pyrrole-2,5-dione, and demonstrate how fluorescence quenching in polar protic solvents is caused by electron driven proton transfer from the solvent to the fluorophore. Armed with this knowledge, the present study acts as a first step for the rational design of future maleimides, potentially moving toward creating a universal fluorophore with tunable efficiency, dependent on environment.

To explore the effects of ring substitution on dissociation dynamics, the primary photochemistry of 2-ethylpyrrole was explored using ultrafast ion imaging techniques. Photoexcitation to the S 1 state, a πσ* state, in the range from 238 to 265 nm results in cleavage of the N-H bond with an H atom appearance lifetime of ca. 70 fs. The insensitivity of this lifetime to photon energy, combined with a small kinetic isotope effect, suggests that tunneling does not play a major role in N-H bond cleavage. Total kinetic energy release spectra reveal modest vibrational excitation in the radical counter-fragment, increasing with photon energy. At wavelengths less than or equal to 248 nm, an additional low kinetic energy H atom loss mechanism becomes available with an appearance lifetime of ∼1.5 ps, possibly due to the population of higher-lying 1 ππ* states.

The relationship between exposure to ultraviolet (UV) radiation and skin cancer urges the need for extra photoprotection, which is presently provided by widespread commercially available sunscreen lotions. Apart from having a large absorption cross section in the UVA and UVB regions of the electromagnetic spectrum, the chemical absorbers in these photoprotective products should also be able to dissipate the excess energy in a safe way, i.e. without releasing photoproducts or inducing any further, harmful, photochemistry. While sunscreens are tested for both their photoprotective capability and dermatological compatibility, phenomena occurring at the molecular level upon absorption of UV radiation are largely overlooked. To date, there is only a limited amount of information regarding the photochemistry and photophysics of these sunscreen molecules. However, a thorough understanding of the intrinsic mechanisms by which popular sunscreen molecular constituents dissipate excess energy has the potential to aid in the design of more efficient, safer sunscreens. In this review, we explore the potential of using gas-phase frequency- and time-resolved spectroscopies in an effort to better understand the photoinduced excited-state dynamics, or photodynamics , of sunscreen molecules. Complementary computational studies are also briefly discussed. Finally, the future outlook of expanding these gas-phase studies into the solution phase is considered.

Methyl-E-4-methoxycinnamate (E-MMC) is a model chromophore of the commonly used commercial sunscreen agent, 2-ethylhexyl-E-4-methoxycinnamate (E-EHMC). In an effort to garner a molecular-level understanding of the photoprotection mechanisms in operation with E-EHMC, we have used time-resolved pump-probe spectroscopy to explore E-MMC's and E-EHMC's excited state dynamics upon UV-B photoexcitation to the S 1 (1 1 ππ*) state in both the gas- and solution-phase. In the gas-phase, our studies suggest that the excited state dynamics are driven by non-radiative decay from the 1 1 ππ* to the S 3 (1 1 nπ*) state, followed by de-excitation from the 1 1 nπ* to the ground electronic state (S 0 ). Using both a non-polar-aprotic solvent, cyclohexane, and a polar-protic solvent, methanol, we investigated E-MMC and E-EHMC's photochemistry in a more realistic, 'closer-to-shelf' environment. A stark change to the excited state dynamics in the gas-phase is observed in the solution-phase suggesting that the dynamics are now driven by efficient E/Z isomerisation from the initially photoexcited 1 1 ππ* state to S 0 .

H atom loss following near ultraviolet photoexcitation of gas phase 2-thiophenethiol molecules has been studied experimentally, by photofragment translational spectroscopy (PTS) methods, and computationally, by ab initio electronic structure calculations. The long wavelength (277.5 ≥ λ(phot) ≥ 240 nm) PTS data are consistent with S-H bond fission after population of the first (1)πσ* state. The partner thiophenethiyl (R) radicals are formed predominantly in their first excited Ã(2)A' state, but assignment of a weak signal attributable to H + R(X˜(2)A'') products allows determination of the S-H bond strength, D0 = 27,800 ± 100 cm(-1) and the Ã-X˜ state splitting in the thiophenethiyl radical (ΔE = 3580 ± 100 cm(-1)). The deduced population inversion between the à and X˜ states of the radical reflects the non-planar ground state geometry (wherein the S-H bond is directed near orthogonal to the ring plane) which, post-photoexcitation, is unable to planarise sufficiently prior to bond fission. This dictates that the dissociating molecules follow the adiabatic fragmentation pathway to electronically excited radical products. π* ← π absorption dominates at shorter excitation wavelengths. Coupling to the same (1)πσ* potential energy surface (PES) remains the dominant dissociation route, but a minor yield of H atoms attributable to a rival fragmentation pathway is identified. These products are deduced to arise via unimolecular decay following internal conversion to the ground (S0) state PES via a conical intersection accessed by intra-ring C-S bond extension. The measured translational energy disposal shows a more striking change once λ(phot) ≤ 220 nm. Once again, however, the dominant decay pathway is deduced to be S-H bond fission following coupling to the (1)πσ* PES but, in this case, many of the evolving molecules are deduced to have sufficiently near-planar geometries to allow passage through the conical intersection at extended S-H bond lengths and dissociation to ground (X˜) state radical products. The present data provide no definitive evidence that complete ring opening can compete with fast S-H bond fission following near UV photoexcitation of 2-thiophenethiol.

Eumelanin is a naturally synthesized ultraviolet light absorbing biomolecule, possessing both photoprotective and phototoxic properties. We infer insight into these properties of eumelanin using a bottom-up approach, by investigating an ultraviolet absorbing motif of eumelanin, 4-tert-butylcatechol. Utilizing a combination of femtosecond transient electronic absorption spectroscopy and time-resolved velocity map ion imaging, our results suggest an environmental-dependent relaxation pathway, following irradiation at 267 nm to populate the S1 ((1)ππ*) state. Gas-phase and nonpolar solution-phase measurements reveal that the S1 state decays primarily through coupling onto the S2 ((1)πσ*) state which is dissociative along the nonintramolecular hydrogen bonded "free" O-H bond. This process occurs in 4.9 ± 0.6 ps in the gas-phase and 18 ± 1 ps in the nonpolar cyclohexane solution. Comparative studies on the deuterated isotopologue of 4-tert-butylcatechol in both the gas- and solution-phase (cyclohexane) reveal kinetic isotope effects of ∼19 and ∼4, respectively, supportive of O-H dissociation along a barriered pathway, and potentially mediated by quantum tunneling. In contrast, in the polar solvent acetonitrile, the S1 state decays on a much longer time scale of 1.7 ± 0.1 ns. We propose that the S1 decay is now multicomponent, driven by internal conversion, intersystem crossing, and fluorescence, as well as O-H dissociation. The attribution of conformer-driven excited state dynamics to explain how the S1 state decays in the gas- and nonpolar solution-phase versus the polar solution-phase, demonstrates the influence the environment can have on the ensuing excited state dynamics.

The dynamics of photoexcited 2,4-dimethylpyrrole (DMP) were studied using time-resolved velocity map imaging spectroscopy over a range of photoexcitation wavelengths (276-238 nm). Two dominant H atom elimination channels were inferred from the time-resolved total kinetic energy release spectra, one which occurs with a time constant of ∼120 fs producing H atoms with high kinetic energies centered around 5000-7000 cm(-1) and a second channel with a time constant of ∼3.5 ps producing H atoms with low kinetic energies centered around 2500-3000 cm(-1). The first of these channels is attributed to direct excitation from the ground electronic state (S0) to the dissociative 1(1)πσ* state (S1) and subsequent N-H bond fission, moderated by a reaction barrier in the N-H stretch coordinate. In contrast to analogous measurements in pyrrole (Roberts et al. Faraday Discuss. 2013, 163, 95-116), the N-H dissociation times are invariant with photoexcitation wavelength, implying a relatively flatter potential in the vertical Franck-Condon region of the 1(1)πσ* state of DMP. The origins of the second channel are less clear-cut, but given the picosecond time constant for this process, we posit that this channel is indirect and is likely a consequence of populating higher-lying electronic states [e.g., 2(1)πσ* (S2)] which, following vibronic coupling into lower-lying intermediary states (namely, S1 or S0), leads to prompt N-H bond fission.

The photoinduced dynamics of the lignin building blocks syringol, guaiacol, and phenol were studied using time-resolved ion yield spectroscopy and velocity map ion imaging. Following irradiation of syringol and guaiacol with a broad-band femtosecond ultraviolet laser pulse, a coherent superposition of out-of-plane OH torsion and/or OMe torsion/flapping motions is created in the first excited (1)ππ* (S1) state, resulting in a vibrational wavepacket, which is probed by virtue of a dramatic nonplanar → planar geometry change upon photoionization from S1 to the ground state of the cation (D0). Any similar quantum beat pattern is absent in phenol. In syringol, the nonplanar geometry in S1 is pronounced enough to reduce the degree of intramolecular H bonding (between OH and OMe groups), enabling H atom elimination from the OH group. For guaiacol, H bonding is preserved after excitation, despite the nonplanar geometry in S1, and prevents O-H bond fission. This behavior affects the propensities for forming undesired phenoxyl radical sites in these three lignin chromophores and provides important insight into their relative "photostabilities" within the larger biopolymer.

The excited state dynamics of resorcinol (1,3-dihydroxybenzene) following UV excitation at a range of pump wavelengths, 278 ≥ λ ≥ 255 nm, have been investigated using a combination of time-resolved velocity map ion imaging and ultrafast time-resolved ion yield measurements coupled with complementary ab initio calculations. After excitation to the 1(1)ππ* state we extract a timescale, τ1, for excited state relaxation that decreases as a function of excitation energy from 2.70 ns to ~120 ps. This is assigned to competing relaxation mechanisms. Tunnelling beneath the 1(1)ππ*/(1)πσ* conical intersection, followed by coupling onto the dissociative (1)πσ* state, yields H atoms born with high kinetic energy (~5000 cm(-1)). This mechanism is in competition with an internal conversion process that is able to transfer population from the photoexcited 1(1)ππ* state back to a vibrationally excited ground state, S0*. When exciting between 264-260 nm a second decay component, τ2, is observed and we put forth several possible explanations as to the origins of τ2, including conformer specific dynamics. Excitation with 237 nm light (above the 1(1)ππ*/(1)πσ* conical intersection) yields high kinetic energy H atoms (~11,000 cm(-1)) produced in ~260 fs, in line with a mechanism involving ultrafast coupling between the 1(1)ππ* (or 2(1)ππ*) and (1)πσ* state followed by dissociation. The results presented highlight the profound effect the presence of additional functional groups, and more specifically the precise location of the functional groups, can have on the excited state dynamics of model heteroaromatic systems following UV excitation.

We present new evidence for the existence of a near threshold π* shape resonance as a common feature in the photoionization of each isomer of difluorobenzene. Experimentally, this is revealed by significant changes in the anisotropy of the photoelectron angular distributions (PADs) following the ionization of the optically aligned S1 state of these molecules at varying photon energies. Continuum multiple scattering Xα calculations reproduce this behaviour well, and allow the visualisation of the continuum shape resonances. The resonances are unusually narrow in energy (<1 eV), but nevertheless appear to extend right down to the ionization thresholds--exactly the low energy range typically accessed in laser-based resonance enhanced multiphoton ionization (REMPI) schemes. The anticipation of such pronounced energy dependence in the PADs and cross-sections sought for other molecules, and an ability to accurately predict such features, should be important for the reliable application and interpretation of experiments involving REMPI probing of those molecules.

In this article we present photoelectron spectra and angular distributions in which ion rotational states are resolved. This data enables the comparison of direct and threshold photoionization techniques. We also present angle-resolved photoelectron signals at different total energies, providing a method to scan the structure of the continuum in the near-threshold region. Finally, we have studied the influence of vibrational excitation on the photoionization dynamics.

We present, for the first time, rotationally resolved photoelectron images resulting from the ionization of a polyatomic molecule. Photoelectron angular distributions pertaining to the formation of individual rotational levels of NH3+ have been extracted from the images and analyzed to enable a complete determination of the radial dipole matrix elements and relative phases that describe the ionization dynamics. This determination leads to the deduction of significantly different dynamics from those extracted in previous studies which lacked either angular information or rotational resolution.