An electron-ion coincidence spectrometer for commissioning of a synchrotron radiation beamline: Absolute photon intensity and content of higher harmonic radiation.

We describe the commissioning of a new electron-ion coincidence spectrometer used to diagnose the photon beam from a plane grating monochromator beamline at the ASTRID2 synchrotron radiation facility. The spectrometer allows determination of the absolute photon intensity by calibration to the photoabsorption cross sections of known gases, such as the rare gases Ar, Kr, and Xe presented here. The spectrometer operates at very low pressure (∼10-8-10-9 mbar) and-due to the coincidence electron-ion detection scheme-the detector efficiencies can be determined routinely; hence, the spectrometer can be recalibrated swiftly. By variation of a single potential of the spectrometer, the content of higher order radiation in the monochromatized synchrotron radiation can be analyzed. The layout and operation of the synchrotron radiation beamline at ASTRID2 and its additional photon diagnostic units are additionally described.

Light Driven Ultrafast Bioinspired Molecular Motors: Steering and Accelerating Photoisomerization Dynamics of Retinal.

Photoisomerization of retinal protonated Schiff base in microbial and animal rhodopsins are strikingly ultrafast and highly specific. Both protein environments provide conditions for fine-tuning the photochemistry of their chromophores. Here, by combining time-resolved action absorption spectroscopy and high-level electronic structure theory, we show that similar control can be gained in a synthetically engineered retinal chromophore. By locking the dimethylated retinal Schiff base at the C11═C12 double bond in its trans configuration (L-RSB), the excited-state decay is rendered from a slow picosecond to an ultrafast subpicosecond regime in the gas phase. Steric hindrance and pretwisting of L-RSB are found to be important for a significant reduction in the excited-state energy barriers, where isomerization of the locked chromophore proceeds along C9═C10 rather than the preferred C11═C12 isomerization path. Remarkably, the accelerated excited-state dynamics also becomes steered. We show that L-RSB is capable of unidirectional 360° rotation from all-trans to 9-cis and from 9-cis to all-trans in only two distinct steps induced by consecutive absorption of two 600 nm photons. This opens a way for the rational design of red-light-driven ultrafast molecular rotary motors based on locked retinal chromophores.

Tuning fast excited-state decay by ligand attachment in isolated chlorophyll a.

Excited-state dynamics plays a key role for light harvesting and energy transport in photosynthetic proteins but it is nontrivial to separate the intrinsic photophysics of the light-absorbers (chlorophylls) from interactions with the protein matrix. Here we study chlorophyll a (4-coordinate complex) and axially ligated chlorophyll a (5-coordinate complex) isolated in vacuo applying mass spectrometry to shed light on the intrinsic dynamics in the absence of nearby chlorophylls, carotenoids, amino acids, and water molecules. The 4-coordinate complexes are tagged by quaternary ammonium ions while the charge is provided by a formate ligand in the case of 5-coordinate complexes. Regardless of excitation to the Soret band or the Q band, a fast ps decay is observed, which is ascribed to the decay of the lowest excited singlet state either by intersystem crossing (ISC) to nearby triplet states or by excited-state relaxation on the excited-state potential-energy surface. The lifetime of the first excited state is 15 ps with Mg2+ at the chlorophyll center, but only 1.7 ps when formate is attached to Mg2+. When the Soret band is excited, an initial sup-ps relaxation is observed which is ascribed to fast internal conversion to the first excited state. With respect to ISC, two factors seem to play a role for the reduced lifetime of the formate-chlorophyll complex: (i) The Mg ion is pulled out of the porphyrin plane thus reducing the symmetry of the chromophore, and (ii) the first excited state (Q band) and T3 are tuned almost into resonance by the ligand, which increases the singlet-triplet mixing.

Spectroscopy and photoisomerization of protonated Schiff-base retinal derivatives in vacuo.

The protonated Schiff-base retinal acts as the chromophore in bacteriorhodopsin as well as in rhodopsin. In both cases, photoexcitation initializes fast isomerization which eventually results in storage of chemical energy or signaling. The details of the photophysics for this important chromophore is still not fully understood. In this study, action-absorption spectra and photoisomerization dynamics of three retinal derivatives are measured in the gas phase and compared to that of the protonated Schiff-base retinal. The retinal derivatives include C9C10trans-locked, C13C14trans-locked and a retinal derivative without the ß-ionone ring. The spectroscopy as well as the isomerization speed of the chromophores are altered significantly as a consequence of the steric constraints.

The reaction of isotope-substituted hydrated iodide I(HO)- with ozone: the reactive influence of the solvent water molecule.

We report an investigation of the reaction of isotope-substituted hydrated iodide I(HO)- with ozone 16O3 to examine the involvement of the water molecules in the oxidation reactions that terminate with the formation of IO3-. Experimentally, we studied the reaction in the gas phase as elementary reactions using a radio-frequency (RF) ion-trap combined with a quadrupole mass spectrometer (QMS). In approximately 1.2% of the reactions of I(HO)- and 16O3, the 18O atom is found to appear in iodine oxide anions, thus giving evidence for a close involvement of the water molecule in a non-negligible number of the reactions towards IO3-. As a part of the experimental investigation, the reaction rate constant for the exchange reaction I(HO)- + HO → I(HO)- + HO at 300 K was found to be (1.3 ± 0.1) × 10-8 cm3 s-1. Quantum chemical calculations are exploited to establish the energetic difference between I(HO)- and I(HO)-.

Reply to the 'Comment on "Atmospheric chemistry of iodine anions: elementary reactions of I-, IO-, and IO with ozone studied in the gas-phase at 300 K using an ion trap"' by D. Britz, Phys. Chem. Chem. Phys., 2019, 21, C9CP03851E.

We reply to the comment by Dieter Britz on two recent papers in Physical Chemistry Chemical Physics. The comment presents a valuable, however, less flexible, alternative to the analysis performed in these papers and as such has no impact on any of the scientific results reported in the two publications.

The reaction of hydrated iodide I(H2O)- with ozone: a new route to IO2- products.

We report on an experimental characterization of the isolated reaction of hydrated iodide I(H2O)- with ozone O3 at room temperature performed using a radio-frequency ion trap combined with a quadrupole mass spectrometer. Contrary to the oxidation reaction of the bare I- ion, the hydrated iodide I(H2O)- primarily reacts to form I- and IO2- with significant absolute reaction rate constants of 2.0 ± 0.3 × 10-10 cm3 molecule-1 s-1 and 2.5 ± 0.3 × 10-10 cm3 molecule-1 s-1 while direct pathways to IO- and IO3- are much weaker. Quantum chemical calculations indicate that in aqueous phase and for atmospherically relevant temperatures, the presence of hydrated iodides are favored over bare I- ions, thus suggesting that the chemistry of the hydrated ions is relevant for understanding and modeling atmospheric processes at the air-water interface.

Atmospheric chemistry of iodine anions: elementary reactions of I-, IO-, and IO2- with ozone studied in the gas-phase at 300 K using an ion trap.

Using a radio-frequency ion trap to study ion-molecule reactions under isolated conditions, we report a direct experimental determination of reaction rate constants for the sequential oxidation of iodine anions by ozone at room temperature (300 K). The results are R1: I- + O3 → IO- + O2, k1 = (7 ± 2) × 10-12 cm3 s-1; R2: IO- + O3 → IO2- + O2, k2 = (10 ± 2) × 10-9 cm3 s-1; R3: IO2- + O3 → IO3- + O2, k3 = (16 ± 2) × 10-9 cm3 s-1. More oxidized forms such as IO4- and IO5- were not observed. Additionally, we performed quantum chemical calculations to elucidate the energetics of these oxidation reactions.

Analysis of ionic photofragments stored in an electrostatic storage ring.

A new method to analyze the properties of fragment ions created in storage ring experiments is presented. The technique relies on an acceleration of ionic fragments immediately after production whereby the fragments are stored in the storage ring. To obtain a fragment mass spectrum, the storage ring is exploited as an electrostatic analyzer (ESA) in which case the number of stored fragment ions is recorded as a function of the applied acceleration potential. However, the storage ring can additionally be employed as a time-of-flight (TOF) instrument by registering the temporal distribution of fragment ions. It is demonstrated that the combined ESA-TOF operation of the ring allows not only to determine fragment masses with much better resolution compared to the ESA mode alone but also enables the extraction of detailed information on the fragmentation dynamics. The method is described analytically and verified with photodissociation experiments on stored Cl2 (-) at an excitation wavelength of 530 nm.

The impact of modeling nuclear fragmentation on delivered dose and radiobiology in ion therapy.

The importance of nuclear interactions for ion therapy arises from the influence of the particle spectrum on, first, radiobiology and therefore also on treatment planning, second, the accuracy of measuring dose and, third, the delivered dose distribution. This study tries to determine the qualitative as well as the quantitative influence of the modeling of inelastic nuclear interactions on ion therapy. Thereby, three key disciplines are investigated, namely dose delivery, dose assessment and radiobiology. In order to perform a quantitative analysis, a relative comparison between six different descriptions of nuclear interactions is carried out for carbon ions. The particle transport is simulated with the Monte Carlo code SHIELD-HIT10A while dose planning and radiobiology are covered by the analytic treatment planning program for particles TRiP, which determines the relative biological effectiveness (RBE) with the local effect model. The obtained results show that the physical dose distribution can in principle be significantly influenced by the modeling of fragmentation (about 10% for a 20% change in all inelastic nuclear cross sections for a target volume ranging from 15 to 25 cm). While the impact of nuclear fragmentation on stopping power ratios can be neglected, the fluence correction factor may be influenced by the applied nuclear models. In contrast to the results for the physical dose, the variation of the RBE is only small (about 1% for a 20% change in all inelastic nuclear cross sections) suggesting a relatively weak dependence of radiobiology on the detailed composition of the particle energy spectrum of the mixed radiation field. Also, no significant change (about 0.2 mm) of the lateral penumbra of the RBE-weighted dose is observed.