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The diarylethene chromophore is commonly used in light-triggered molecular switches. The chromophore undergoes reversible 6π-electrocyclisation (ring closing) and cycloreversion (ring opening) reactions upon exposure to UV and visible light, respectively, providing bidirectional photoswitching. Here, we investigate the gas-phase photoisomerisation of meta- (m) and para- (p) substituted dithienylethene carboxylate anions (DTE −) using tandem ion mobility mass spectrometry coupled with laser excitation. The ring-closed forms of p-DTE − and m-DTE − are found to undergo cycloreversion in the gas phase with maximum responses associated with bands in the visible (λ max ≈ 600 nm) and the ultraviolet (λ max ≈ 360 nm). The ring-open p-DTE − isomer undergoes 6π-electrocyclisation in the ultraviolet region at wavelengths shorter than 350 nm, whereas no evidence is found for the corresponding electrocyclisation of ring-open m-DTE −, a situation attributed to the fact that the antiparallel geometry required for electrocyclisation of m-DTE − is energetically disfavoured. This highlights the influence of the carboxylate substitution position on the photochemical properties of DTE molecules. We find no evidence for the formation in the gas phase of the undesirable cyclic byproduct, which causes fatigue of DTE photoswitches in solution.

We report cryogenic vibrational spectra of gas-phase cations of two common hydroxycoumarins, scopoletin and esculetin, as well as their glycosidic derivatives, scopolin and esculin. The study allows direct observation of the intramolecular interactions between the hydroxyl groups of these molecules. We use cryogenic messenger-tagging IR action spectroscopy to detect vibrational bands in the 3100-3800 cm(-1 )spectral range and discuss the corresponding structural characteristics and hydrogen bonding networks that they imply. The experimental data are supported by a thorough computational evaluation, including investigation of the conformational space. Through comparison of the calculated conformers with the experimental results, we identify the main types of OH oscillators and infer how protonation and sodiation affect the structural arrangement of these molecules. The results presented here provide direct evidence of how slight structural differences sensitively affect the hydrogen bonding network in coumarin derivatives.

Molecular photoswitches based on the norbornadiene–quadricylane (NBD–QC) couple have been proposed as key elements of molecular solar thermal energy storage schemes. To characterize the intrinsic properties of such systems, reversible isomerization of a charge-tagged NBD–QC carboxylate couple is investigated in a tandem ion mobility mass spectrometer, using light to induce intramolecular [2 + 2] cycloaddition of NBD carboxylate to form the QC carboxylate and driving the back reaction with molecular collisions. The NBD carboxylate photoisomerization action spectrum recorded by monitoring the QC carboxylate photoisomer extends from 290 to 360 nm with a maximum at 315 nm, and in the longer wavelength region resembles the NBD carboxylate absorption spectrum recorded in solution. Key structural and photochemical properties of the NBD–QC carboxylate system, including the gas-phase absorption spectrum and the energy storage capacity, are determined through computational studies using density functional theory.

Given the biological relevance and intrinsic structural complexity of glycans, increasing efforts are being directed towards developing a general glycan database that includes information from different analytical methods. As recently demonstrated, cryogenic infrared (IR) spectroscopy is a promising technique for glycan analysis, as it provides unique vibrational finger-prints of specific glycan isomer ions. One of the main goals of a glycan database is the identification and detailed characteri-zation of unknown species. In this work, we combine enzymatic digestion with cryogenic IR-spectroscopy and demonstrate how it can be used for glycan identification. We measured the IR-spectra of a series of cationic glycan standards of increasing complexity and compared them with spectra of the same species after enzymatic cleavage of larger glycans. We show that the cryogenic IR spectra of the cleaved glycans are highly structured and virtually identical to those of standards after both single and multiple cleavages. Our results suggest that the combination of these methods represents a potentially powerful and spe-cific approach for the characterization of unknown glycans.

Electronic spectra are measured for mass-selected C

The photoisomerization behavior of styryl 9M, a common dye used in material sciences, is investigated using tandem ion mobility spectrometry (IMS) coupled with laser spectroscopy. Styryl 9M has two alkene linkages, potentially allowing for four geometric isomers. IMS measurements demonstrate that at least three geometric isomers are generated using electrospray ionization with the most abundant forms assigned to a combination of EE (major) and ZE (minor) geometric isomers, which are difficult to distinguish using IMS as they have similar collision cross sections. Two additional but minor isomers are generated by collisional excitation of the electrosprayed styryl 9M ions and are assigned to the EZ and ZZ geometric isomers, with the latter predicted to have a p-stacked configuration. The isomer assignments are supported through calculations of equilibrium structures, collision cross sections, and statistical isomerization rates. Photoexcitation of selected isomers using an IMS-photo-IMS strategy shows that each geometric isomer photoisomerizes following absorption of near-infrared and visible light, with the EE isomer possessing a S-1

Luciferin molecules are common luminophores found throughout the biological kingdoms. Here, electrospray ionization and tandem ion mobility spectrometry coupled with laser spectroscopy are used to demonstrate that D-luciferin and oxyluciferin deprotonated anions can be produced in two isomeric forms, which can be separated by virtue of their different collision cross sections with a buffer gas. The two isomers possess distinguishable but partially overlapping photodepletion action spectra over the visible range, implying distinct intrinsic absorption profiles. The site of deprotonation and tautomeric forms of the electrosprayed isomers are assigned through comparisons between experimental and calculated collision cross sections and electronic excitation energies. The study clearly shows that electrospray ionization of biochromophore molecules can generate multiple isomeric forms with distinct electronic spectra. Graphic Abstract: [Figure not available: see fulltext.].

Tandem ion mobility mass spectrometry-coupled laser excitation is used to record photodetachment, photoisomerization and photodepletion action spectra for a series of deprotomer-selected hydroxycinnamate anions, including deprotonated caffeic, ferulic and sinapinic acids. This molecular series accounts for most hydroxycinnamic moieties found in nature. Phenoxide deprotomers for para and ortho structural isomers have similar photodetachment action spectra that span the 350 – 460 nm range with the maximum response occurring between 420 and 440 nm. None of the phenoxide deprotomers showed evidence for E $$\rightarrow $$ Z photoisomerization. In contrast, photoexcitation of the carboxylate deprotomers of caffeic and ferulic acids and the meta-phenoxide deprotomer of caffeic acid initiates intramolecular proton transfer to give the para-phenoxide deprotomer. Photoexcitation of the carboxylate deprotomer of sinapinic acid and ortho-coumaric acid does not result in intramolecular proton transfer, presumably due to substantial barriers for rearrangement. For deprotonated meta-coumaric acid, interconversion between the phenoxide and carboxylate deprotomers occurs in the ion mobility spectrometer drift region where the effective ion temperature is $$T_{eff}\approx $$ 299 K.

Superhydrogenated polycyclic aromatic hydrocarbons (PAHs) have been suggested to catalyze the formation of H2 in certain regions of space, but it remains unclear under which circumstances this mechanism is viable given the reduced carbon backbone stability of superhydrogenated PAHs. We report a laboratory study on the stability of the smallest pericondensed PAH, pyrene (C16H10+N , with N = 4, 6, and 16 additional H atoms), against photodestruction by single vacuum ultraviolet photons using the photoelectron–photoion coincidence technique. For N = 4, we observe a protective effect of hydrogenation against the loss of native hydrogens, in the form of an increase in the appearance energies of the and C16H8 + daughter ions compared to those reported for pristine pyrene (C16H10). No such effect is seen for N = 6 or 16, where the weakening effect of replacing aromatic bonds with aliphatic ones outweighs the buffering effect of the additional hydrogen atoms. The onset of fragmentation occurs at similar internal energies for N = 4 and 6, but is significantly lower for N = 16. In all three cases, H-loss and C m H n -loss (m ≥ 1, carbon backbone fragmentation) channels open at approximately the same energy. The branching fractions of the primary channels favor H-loss for N = 4, C m H n -loss for N = 16, and are roughly equal for the intermediate N = 6. We conclude that superhydrogenated pyrene is probably too small to support catalytic H2-formation, while trends in the current and previously reported data suggest that larger PAHs may serve as catalysts up to a certain level of hydrogenation.

The European physical journal / D 75(5), 152 (2021). doi:10.1140/epjd/s10053-021-00155-y, This roadmap article highlights recent advances, challenges and future prospects in studies of the dynamics of molecules and clusters in the gas phase. It comprises nineteen contributions by scientists with leading expertise in complementary experimental and theoretical techniques to probe the dynamics on timescales spanning twenty order of magnitudes, from attoseconds to minutes and beyond, and for systems ranging in complexity from the smallest (diatomic) molecules to clusters and nanoparticles. Combining some of these techniques opens up new avenues to unravel hitherto unexplored reaction pathways and mechanisms, and to establish their significance in, e.g. radiotherapy and radiation damage on the nanoscale, astrophysics, astrochemistry and atmospheric science., Published by Springer, Heidelberg

Chemical reaction dynamics are studied to monitor and understand the concerted motion of several atoms while they rearrange from reactants to products. When the number of atoms involved increases, the number of pathways, transition states and product channels also increases and rapidly presents a challenge to experiment and theory. Here we disentangle the dynamics of the competition between bimolecular nucleophilic substitution (S

Infrared and electronic spectra are indispensable for understanding the structural and energetic properties of charged molecules and clusters in the gas phase. However, the presence of isomers can potentially complicate the interpretation of spectra, even if the target molecules or clusters are mass-selected beforehand. Here, we describe an instrument for spectroscopically characterizing charged molecular clusters that have been selected according to both their isomeric form and their mass-to-charge ratio. Cluster ions generated by laser ablation of a solid sample are selected according to their collision cross sections with helium buffer gas using a drift tube ion mobility spectrometer and their mass-to-charge ratio using a quadrupole mass filter. The mobility- and mass-selected target ions are introduced into a cryogenically cooled, three-dimensional quadrupole ion trap where they are thermalized through inelastic collisions with an inert buffer gas (He or He/N2 mixture). Spectra of the molecular ions are obtained by tagging them with inert atoms or molecules (Ne and N2), which are dislodged following resonant excitation of an electronic transition, or by photodissociating the cluster itself following absorption of one or more photons. An electronic spectrum is generated by monitoring the charged photofragment yield as a function of wavelength. The capacity of the instrument is illustrated with the resonance-enhanced photodissociation action spectra of carbon clusters ([Formula: see text]) and polyacetylene cations (HC2 nH+) that have been selected according to the mass-to-charge ratio and collision cross section with He buffer gas and of mass-selected [Formula: see text] and Au2Ag+ clusters.

Time-resolved spontaneous and laser-induced unimolecular fragmentation of perylene cations (C20H12+) has been measured on timescales up to 2 s in a cryogenic electrostatic ion beam storage ring. We elaborate a quantitative model, which includes fragmentation in competition with radiative cooling via both vibrational and electronic (recurrent fluorescence) de-excitation. Excellent agreement with experimental results is found when sequential fragmentation of daughter ions co-stored with the parent perylene ions is included in the model. Based on the comparison of the model to experiment, we constrain the oscillator strength of the D-1 -> D-0 emissive electronic transition in perylene (f(RF) = 0.055 +/- 0.011), as well as the absolute absorption cross section of the D-5 670 Mb). The former transition is responsible for the laser-induced and recurrent fluorescence of perylene, and the latter is the most prominent in the absorption spectrum. The vibrational cooling rate is found to be consistent with the simple harmonic cascade approximation. Quantitative experimental benchmarks of unimolecular processes in polycyclic aromatic hydrocarbon ions like perylene are important for refining astrochemical models.

Despite the essential role that glycans play in many biological processes, their isomeric com-plexity makes their structural determination partic-ularly challenging. Tandem mass spectrometry has played a central role in glycan analysis, and recent work has shown that fragments generated by colli-sion-induced dissociation (CID) of disaccharides can retain the anomeric configuration of the glyco-sidic bond. If this result proves to be general, it would provide a powerful new tool for glycan se-quencing. In this work, we use messenger-tagging infrared (IR) spectroscopy to investigate the gener-ality of anomer retention in CID by exploring dif-ferent fragmentation channels in glycans of in-creasing complexity. Our results demonstrate that anomericity seems to be retained irrespective of fragment size and branching.

Donor-acceptor Stenhouse adducts (DASAs) are a new class of photoswitching molecules with excellent fatigue resistance and synthetic tunability. Here, tandem ion mobility mass spectrometry coupled with laser excitation is used to characterize the photocyclization reaction of isolated, charge-tagged DASA molecules over the 450-580 nm range. The experimental maximum response at 530 nm agrees with multireference perturbation theory calculations for the S1 ← S0 transition maximum at 533 nm. Photocyclization in the gas phase involves absorption of at least two photons; the first photon induces Z-E isomerization from the linear isomer to metastable intermediate isomers, while the second photon drives another E-Z isomerization and 4π-electrocyclization reaction. Cyclization is thermally reversible in the gas phase with collisional excitation.

Electronic spectra are measured for mass-selected C+2( = 6–14) clusters over the visible and near-infrared spectral range through resonance enhanced photodissociation of clusters tagged with N2 molecules in a cryogenic ion trap. The carbon cluster cations are generated through laser ablation of a graphite disk and can be selected according to their collision cross section with He buffer gas and their mass prior to being trapped and spectroscopically probed. The data suggest that the C+2( = 6–14) clusters have monocyclic structures with bicyclic structures becoming more prevalent for C+22 and larger clusters. The C+2 electronic spectra are dominated by an origin transition that shifts linearly to a longer wavelength with the number of carbon atoms and associated progressions involving excitation of ring deformation vibrational modes. Bands for C+12, C+16, C+20, C+24, and C+28 are relatively broad, possibly due to rapid non-radiative decay from the excited state, whereas bands for C+14, C+18, C+22, and C+26 are narrower, consistent with slower non-radiative deactivation.

The effect of steric hindrance on the stereodynamics of nucleophilic substitution (SN2) and base-induced elimination (E2) has been studied using crossed-beam velocity map imaging., Nucleophilic substitution (SN2) and base-induced elimination (E2), two indispensable reactions in organic synthesis, are commonly assumed to proceed under stereospecific conditions. Understanding the way in which the reactants pre-orient in these reactions, that is its stereodynamics, is essential in order to achieve a detailed atomistic picture and control over such processes. Using crossed beam velocity map imaging, we study the effect of steric hindrance in reactions of Cl– and CN– with increasingly methylated alkyl iodides by monitoring the product ion energy and scattering angle. For both attacking anions the rebound mechanism, indicative of a direct SN2 pathway, is found to contribute to the reaction at high relative collision energies despite being increasingly hindered. An additional forward scattering mechanism, ascribed to a direct E2 reaction, also contributes at these energies. Inspection of the product energy distributions confirms the direct and fast character of both mechanisms as opposed to an indirect reaction mechanism which leads to statistical energy redistribution in the reaction complex. This work demonstrates that nonstatistical dynamics and energetics govern SN2 and E2 pathways even in sterically hindered exchange reaction systems.

Because of their high photoisomerization efficiencies, azobenzenes and their functionalized derivatives are used in a broad range of molecular photoswitches. Here, the photochemical properties of the trans isomers of protonated azobenzene (ABH+) and protonated 4-aminoazobenzene (NH2ABH+) cations are investigated in the gas phase using a tandem ion mobility spectrometer. Both cations display a strong photoisomerization response across their S1 ← S0 bands, with peaks in their photoisomerization yields at 435 and 525 nm, respectively, red-shifted with respect to the electronic absorption bands of the unprotonated AB and NH2AB molecules. The experimental results are interpreted with the aid of supporting electronic structure calculations considering the relative stabilities and geometries of the possible isomers and protomers and vertical electronic excitation energies.

The photoisomerisation of charged molecules in solution is probed directly using ion mobility mass spectrometry with electrospray ionisation. The technique is demonstrated using a prototype azoheteroarene cation in methanol. By scanning the wavelength of the excitation light while monitoring the photoisomer intensity a photoisomerisation action spectrum is generated, which, when compared with a conventional absorption spectrum, allows the relative photoisomerisation quantum yield to be determined across a range of wavelengths.

Indigoid chromophores have emerged as versatile molecular photoswitches, offering efficient reversible photoisomerization upon exposure to visible light. Here we report synthesis of a new class of permanently charged hemiindigos (HIs) and characterization of photochemical properties in gas phase and solution. Gas‐phase studies, which involve exposing mobility‐selected ions in a tandem ion mobility mass spectrometer to tunable wavelength laser radiation, demonstrate that the isolated HI ions are photochromic and can be reversibly photoswitched between Z and E isomers. The Z and E isomers have distinct photoisomerization response spectra with maxima separated by 40–80 nm, consistent with theoretical predictions for their absorption spectra. Solvation of the HI molecules in acetonitrile displaces the absorption bands to lower energy. Together, gas‐phase action spectroscopy and solution NMR and UV/Vis absorption spectroscopy represent a powerful approach for studying the intrinsic photochemical properties of HI molecular switches., Charge‐tagged hemiindigo photoswitches are demonstrated to undergo reversible Z/E photoisomerization in the gas phase, proving that photoinduced structural rearrangements do not rely on a solvent but rather reflect the intrinsic characteristics of the photoswitches.

Ultraslow radiative cooling lifetimes and adiabatic detachment energies for three astrochemically relevant anions, C

Deprotonated para-coumaric acid is commonly considered as a model for the chromophore in photoactive yellow protein, which undergoes E → Z isomerization following absorption of blue light. Here, tandem ion mobility mass spectrometry is coupled with laser excitation to study the photochemistry of deprotonated para-coumaric acid, to show that the E isomers of the phenoxide and carboxylate forms have distinct photochemical responses with maxima in their action spectra at 430 and 360 nm, respectively. The E isomer of the phenoxide anion undergoes efficient autodetachment upon excitation of its lowest ππ* transition. For the E isomer of the carboxylate deprotomer, a one-way photoinitiated proton transfer generates the phenoxide deprotomer through a mechanism postulated to involve an excited-state enol–keto tautomerism followed by a series of ground-state rearrangements including a second proton transfer. This mechanism is supported by experiments in which the relevant intermediate keto isomer is prepared and spectroscopically probed and through master equation modeling of possible ground-state isomerization processes. The Z isomer of the carboxylate deprotomer shows a weak Z → E photoisomerization response that occurs in competition with photodestruction (presumably electron detachment), demonstrating that the E and Z isomers undergo different processes in their excited states. The study highlights the utility of isomer-selective spectroscopy for characterizing the photochemistry of isolated anions possessing multiple deprotonation sites.

Substituted naphthalene anions (deprotonated 2-naphthol and 6-hydroxy-2-naphthoic acid) are spectroscopically probed in a tandem drift tube ion mobility spectrometer (IMS). Target anions are selected according to their drift speed through nitrogen buffer gas in the first IMS stage before being exposed to a pulse of tunable light that induces either photodissociation or electron photodetachment, which is conveniently monitored by scavenging the detached electrons with trace \ce{SF6} in the buffer gas. The photodetachment action spectrum of the 2-naphtholate anion exhibits a band system spanning 380-460\,nm~with a prominent series of peaks spaced by 440\,\cme, commencing at 458.5\,nm, and a set of weaker peaks near the electron detachment threshold corresponding to transitions to dipole-bound states. The two deprotomers of 6-hydroxy-2-naphthoic acid are separated and spectroscopically probed independently. The molecular anion formed from deprotonation of the hydroxy group possesses a photodetachment action spectrum similar to that of the 2-naphtholate anion with an onset at 470\,nm and a maximum at 420\,nm. Near threshold, photoreaction with \ce{SF6} is observed with displacement of an OH group by an F atom. In contrast, the anion formed from deprotonation of the carboxylic acid group features a photodissociation action spectrum, recorded on the \ce{CO2} loss channel, lying to much shorter wavelength with an onset at 360\,nm and maximum photoresponse at 325\,nm.

Fluorescent proteins have revolutionized the visualization of biological processes, prompting efforts to understand and control their intrinsic photophysics. Here we investigate the photoisomerization of deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI-), the chromophore in green fluorescent protein and in Dronpa protein, where it plays a role in switching between fluorescent and nonfluorescent states. In the present work, isolated HBDI- molecules are switched between the Z and E forms in the gas phase in a tandem ion mobility mass spectrometer outfitted for selecting the initial and final isomers. Excitation of the S1 ← S0 transition provokes both Z → E and E → Z photoisomerization, with a maximum response for both processes at 480 nm. Photodetachment is a minor channel at low light intensity. At higher light intensities, absorption of several photons in the drift region drives photofragmentation, through channels involving CH3 loss and concerted CO and CH3CN loss, although isomerization remains the dominant process.

Ruthenium sulfoxide complexes undergo thermally reversible linkage isomerization of sulfoxide ligands from S- to O-bound in response to light. Here, we report photoisomerization action spectra for a ruthenium bis-sulfoxide molecular photoswitch, [Ru(bpy)2(bpSO)]2+, providing the first direct evidence for photoisomerization of a transition metal complex in the gas phase. The linkage isomers are separated and isolated in a tandem drift tube ion mobility spectrometer and exposed to tunable laser radiation provoking photoisomerization. Direct switching of the S,S-isomer to the O,O-isomer following absorption of a single photon is the predominant isomerization pathway in the gas phase, unlike in solution, where stepwise isomerization is observed with each sulfoxide ligand switching in turn. The change in isomerization dynamics is attributed to rapid vibrational quenching that suppresses isomerization in solution. Supporting electronic structure calculations predict the wavelengths and intensities of the peaks in the photoisomerization action spectra of the S,S- and S,O-isomers, indicating that they correspond to metal-to-ligand charge transfer (MLCT) and ligand-centered ππ* transitions.

Substituted azobenzenes serve as chromophores and actuators in a wide range of molecular photoswitches. Here, tandem ion mobility spectrometry coupled with laser excitation is used to investigate the photoisomerisation of selected E and Z isomers of the charge-tagged azobenzene, methyl orange. Both isomers display a weak S1(nπ*) photoisomerisation response in the blue part of the spectrum peaking at 440 nm and a more intense S2(ππ*) photoisomerisation response in the near-UV with maxima at 370 and 310 nm for the E and Z isomers, respectively. The 60 nm separation between the S2(ππ*) photo-response maxima for the two isomers allows them to be separately addressed in the gas phase and to be reversibly photoisomerised using different colours of light. This is an essential characteristic of an ideal photoswitch. The study demonstrates that a sequence of light pulses at different stages in an ion mobility spectrometer can be deployed to generate and probe isomers that cannot be electrosprayed directly from solution or produced through collisions in the ion source.

In addition to the nucleophile and solvent, the leaving group has a significant influence on SN2 nucleophilic substitution reactions. Its role is frequently discussed with respect to reactivity, but its influence on the reaction dynamics remains unclear. Here, we uncover the influence of the leaving group on the gas-phase dynamics of SN2 reactions in a combined approach of crossed-beam imaging and dynamics simulations. We have studied the reaction F(-) + CH3Cl and compared it to F(-) + CH3I. For the two leaving groups, Cl and I, we find very similar structures and energetics, but the dynamics show qualitatively different features. Simple scaling of the leaving group mass does not explain these differences. Instead, the relevant impact parameters for the reaction mechanisms are found to be crucial and the differences are attributed to the relative orientation of the approaching reactants. This effect occurs on short timescales and may also prevail in solution-phase conditions.

The velocity map imaging method has been applied to crossed beam studies of charge transfer and proton transfer between methyl (CH3) radicals formed by pyrolysis and H3(+) cations over the collision energy range from 1.2 to 3.4 eV. Vibrational excitation in the H3(+) reactants plays an important role both in promoting endoergic charge transfer and in supplying energy to the products of the proton-transfer reaction. Excited H3(+) reactants with vibrational energy in excess of the barrier lead to energy-resonant charge transfer via long-range collisions. A small fraction of collisions that take place at low impact parameters appear to form charge-transfer products with higher levels of internal excitation. The proton-transfer reaction exhibits direct, stripping-like dynamics. Consistent with the kinematics of proton transfer, incremental kinetic energy supplied to the reactants is strongly directed into product relative kinetic energy, as predicted by the concept of "induced repulsive energy release".

A range of ion-molecule reactions have been studied in the last years using the crossed-beam ion imaging technique, from charge transfer and proton transfer to nucleophilic substitution and elimination. This review presents the detailed insights that have been gained with respect to the dynamics of both cation-molecule and anion-molecule reactions studied with this method. In particular, we show the recent progress that has been achieved to understand the atomistic energetics and dynamics of ion-molecule reactions, such as the effects of vibrational quantum states, the formation of carbon-carbon bonds, and the competition between nucleophilic substitution and elimination.

The shapes of many molecules can be transformed by light or heat. Here we investigate collision- and photon-induced interconversions of EE, EZ, and ZZ isomers of the isolated Congo red (CR) dianion, a double molecular switch containing two ─N═N─ azo groups, each of which can have the E or Z configuration. We find that collisional activation of CR dianions drives a one-way ZZ→EZ→EE cascade towards the lowest-energy isomer, whereas the absorption of a single photon over the 270-600 nm range can switch either azo group from E to Z or Z to E, driving the CR dianion to lower- or higher-energy forms. The experimental results, which are interpreted with the aid of calculated statistical isomerization rates, indicate that photoisomerization of CR in the gas phase involves a passage through conical intersection seams linking the excited and ground state potential energy surfaces rather than through isomerization on the ground state potential energy surface following internal conversion.

The charge transfer reaction of Ar

Ultraslow radiative cooling lifetimes and adiabatic detachment energies for three astrochemically relevant anions, Cn- (n = 3-5), are measured using the Double ElectroStatic Ion Ring ExpEriment (DESIREE) infrastructure at Stockholm University. DESIREE maintains a background pressure of approximate to 10(-14) mbar and temperature of approximate to 13 K, allowing storage of mass-selected ions for hours and providing conditions coined a "molecular cloud in a box." Here, we construct two-dimensional (2D) photodetachment spectra for the target anions by recording photodetachment signal as a function of irradiation wavelength and ion storage time (seconds to minute time scale). Ion cooling lifetimes, which are associated with infrared radiative emission, are extracted from the 2D photodetachment spectrum for each ion by tracking the disappearance of vibrational hot-band signal with ion storage time, giving 1e cooling lifetimes of 3.1 +/- 0.1 s (C3-), 6.8 +/- 0.5 s (C4-), and 24 +/- 5 s (C5-). Fits of the photodetachment spectra for cold ions, i.e., those stored for at least 30 s, provide adiabatic detachment energies in good agreement with values from laser photoelectron spectroscopy on jet-cooled anions, confirming that radiative cooling has occurred in DESIREE. Ion cooling lifetimes are simulated using a simple harmonic cascade model, finding good agreement with experiment and providing a mode-by-mode understanding of the radiative cooling properties. The 2D photodetachment strategy and radiative cooling modeling developed in this study could be applied to investigate the ultraslow cooling dynamics of a wide range of molecular anions.

The proton transfer reaction H3(+) + CO is one of the cornerstone chemical processes in the interstellar medium. Here, the dynamics of this reaction have been investigated using crossed beam velocity map imaging. Formyl product cations are found to be predominantly scattered into the forward direction irrespective of the collision energy. In this process, a high amount of energy is transferred to internal product excitation. By fitting a sum of two distribution functions to the measured internal energy distributions, the product isomer ratio is extracted. A small HOC(+) fraction is obtained at a collision energy of 1.8 eV, characterized by an upper limit of 24% with a confidence level of 84%. At lower collision energies, the data indicate purely HCO(+) formation. Such low values are unexpected given the previously predicted efficient formation of both HCO(+) and HOC(+) isomers for thermal conditions. This is discussed in light of the direct reaction dynamics that are observed.

The nucleophilic substitution reaction CN(-) + CH3I allows for two possible reactive approaches of the reactant ion onto the methyl halide, which lead to two different product isomers. Stationary point calculations predict a similar shape of the potential and a dominant collinear approach for both attacks. In addition, an H-bonded pre-reaction complex is identified as a possible intermediate structure. Submerged potential energy barriers hint at a statistical formation process of both CNCH3 and NCCH3 isomers at the experimental collision energies. Experimental angle- and energy differential cross sections show dominant direct rebound dynamics and high internal excitation of the neutral product. No distinct bimodal distributions can be extracted from the velocity images, which impedes the indication of a specific preference towards any of the product isomers. A forward scattering simulation based on the experimental parameters describes accurately the experimental outcome and shows how the possibility to discriminate between the two isomers is mainly hindered by the large product internal excitation.

The charge transfer reaction of Ar+ with H2 and D2 has been investigated in an experiment combining crossed beams with three-dimensional velocity map imaging. Angle-differential cross sections for two collision energies have been obtained for both neutral species. We find that the product ions are highly internally excited. In the reaction with H2, the spin-orbit excited Ar+ state’s coupling to the “resonant” vibrationally excited product H2+ (υ = 2) dominates for both investigated energies, in line with previous investigations. The observed angular distributions, however, show significantly less back-scattering than was found previously. Furthermore, we discovered that the product ions are highly rotationally excited. In the case of Ar+ reacting with D2, the energetically closest lying vibrational levels are not strictly preferred and higher-lying vibrational levels are also populated. For both species, the backward-scattered products show higher internal excitation.

We present the first experimental demonstration of Z↔E photoisomerization the GFP chromophore anion, HBDI−, in the gas phase. In the single photon absorption regime, the photoisomerization action spectra show two maxima at 480 nm and 455 nm. In the multiphoton absorption regime, photodissociation and photodetachment channels modify the appearance of the photoisomerization band. This work provides a new approach to characterize photoisomerization pathways in biomolecular ions.

Electrostatic ion imaging with the velocity map imaging mode is a widely used method in atomic and molecular physics and physical chemistry. In contrast, the spatial map imaging (SMI) mode has received very little attention, despite the fact that it has been proposed earlier [A. T. J. B. Eppink and D. H. Parker, Rev. Sci. Instrum. 68, 3477 (1997)]. Here, we present a detailed parametric characterization of SMI both by simulation and experiment. One-, two- and three-dimensional imaging modes are described. The influence of different parameters on the imaging process is described by means of a Taylor expansion. To experimentally quantify elements of the Taylor expansion and to infer the spatial resolution of our spectrometer, photoionization of toluene with a focused laser beam has been carried out. A spatial resolution of better than 4 μm out of a focal volume of several mm in diameter has been achieved. Our results will be useful for applications of SMI to the characterization of laser beams, the overlap control of multiple particle or light beams, and the determination of absolute collision cross sections.

Orientador: Mariza Corrêa Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Filosofia e Ciências Humanas Resumo: A pesquisa desenvolvida nesta tese de doutoramento tem como eixo central o estudo do naturismo, atividade em que a nudez do corpo é exposta em espaços públicos. Nesta, são discutidos os aspectos centrais que sustentam a perspectiva do processo de construção de identidades relativa ao fenômeno. O naturismo pode ser interpretado como derivado de uma sociedade que, por um lado, cultua o corpo e o poder da sua imagem e, por outro, atribui ao lazer uma função decisiva na promoção de uma ação social ligada a preceitos morais. Como o corpo humano serve de símbolo de pertencimento, investigam-se as dimensões intrínsecas das relações entre os praticantes, tendo sempre em vista a contraposição à ênfase que os grupos naturistas colocam na "pureza" e o "igualitarismo" dos corpos nus. Utilizando a Associação Naturista de Abricó (ANA) do município do Rio de Janeiro (RJ) como objeto de pesquisa, baseia sua investigação na problematização do paradoxo que se inscreve no "respeito" obtido e exigido através da nudez comunal Abstract: The research developed in this doctoral thesis is a study on the central axis of naturism, activity in which the body is exposed naked in public spaces. We discuss the key aspects that support the viewpoint of the construction of identities related to the phenomenon. Naturism can be interpreted as derived from a society that on the one hand, worships the body and the power of its image and, second, gives leisure a decisive role in promoting social action linked to moral precepts. As the human body serves as a symbol of belonging, the intrinsic dimensions of relations among practitioners is investigated, always bearing in mind the opposition emphasized by naturist groups between "purity" and "egalitarianism" of naked bodies. Using Abricó Naturist Association (ANA) in the municipality of Rio de Janeiro (RJ) as a research subject, this research analyses the paradox that is part of the "respect" demanded and obtained through communal nudity Doutorado Ciências Sociais Doutor em Ciências Sociais

Determining the primary structure of glycans remains challenging due to their isomeric complexity. While high-resolution ion mobility spectrometry (IMS) has recently allowed distinguishing between many glycan isomers, the arrival-time distributions (ATDs) frequently exhibit multiple peaks, which can arise from positional isomers, reducing-end anomers, or different conformations. Here, we present the combination of ultrahigh-resolution ion mobility, collision-induced dissociation (CID), and cryogenic infrared (IR) spectroscopy as a systematic method to identify reducing-end anomers of glycans. Previous studies have suggested that high-resolution ion mobility of sodiated glycans is able to separate the two reducing-end anomers. In this case, Y-fragments generated from mobility-separated precursor species should also contain a single anomer at their reducing end. We confirm that this is the case by comparing the IR spectra of selected Y-fragments to those of anomerically pure mono- and disaccharides, allowing the assignment of the mobility-separated precursor and its IR spectrum to a single reducing-end anomer. The anomerically pure precursor glycans can henceforth be rapidly identified on the basis of their IR spectrum alone, allowing them to be distinguished from other isomeric forms.

Abstract Radiative cooling of carbon cluster anions C2n+1− (n = 3–5) is investigated using the cryogenic electrostatic ion storage ring DESIREE. Two different strategies are applied to infer infrared emission on slow (milliseconds to seconds) and ultraslow (seconds to minutes) timescales. Initial cooling of the ions over the millisecond timescale is probed indirectly by monitoring the decay in the yield of spontaneous neutralization by thermionic emission. The observed cooling rates are consistent with a statistical model of thermionic electron emission in competition with infrared photon emission due to vibrational de-excitation. Slower cooling over the seconds to minutes timescale associated with infrared emission from low-frequency vibrational modes is probed using time-dependent action spectroscopy. For C9− and C11−, cooling is evidenced by the time-evolution of the yield of photo-induced neutralization following resonant excitation of electronic transitions near the detachment threshold. The cross-section for resonant photo-excitation is at least two orders of magnitude greater than for direct photodetachment. In contrast, C7− lacks electronic transitions near the detachment threshold. Graphical abstract

Base-induced elimination (E2) and bimolecular nucleophilic substitution (S(N)2) are two of the most versatile reactions that are important in preparative organic chemistry. These stereospecific reactions are often found in direct competition with each other. Elimination can proceed via two distinct transition states, referred to as anti and syn, of which anti is commonly energetically favored. To investigate the intrinsic dynamics of base-induced elimination, reactions under single-collision conditions are required. Here, we present reactive scattering results on the prototype reaction of the fluoride anion with tert-butyl halides. The observed mechanistic fingerprints are associated with the E2 reaction, because steric hindrance at the alpha-carbon suppresses the S(N)2 reaction [Carrascosa, E.; Meyer, J.; Zhang, J.; Stei, M.; Michaelsen, T.; Hase, W. L.; Yang, L.; Wester, R. Nat. Commun. 2017, 8, 25]. The reaction coordinate shows energetically submerged transition states, with anti favored over syn, and we found a very shallow prereaction well for anti. We predominantly found indirect dynamics for a range of collision energies, which can be separated into three remarkably different mechanisms. At low collision energies, the first is a large impact parameter indirect mechanism which leads to a forward-backward symmetric scattering signature. The second mechanism is attributed to low-impact parameter reactions with a near-statistical partitioning of the total available energy. The majority of events are associated with widespread isotropic scattering. Unexpectedly, the product ion kinetic energy distributions are independent of collision energy. We associate this with dynamic trapping in a prereaction well supported by a large centrifugal potential. These measured fingerprints support that atomistic reaction dynamics cannot be predicted based on stationary arguments alone.