Photodetachment Of Anions Research Articles

Photoelectron Velocity Map Imaging Spectroscopy of the Beryllium Trimer and Tetramer.

Computational studies of small beryllium clusters (BeN) predict dramatic, nonmonotonic changes in the bonding mechanisms and per-atom cohesion energies with increasing N. To date, experimental tests of these quantum chemistry models are lacking for all but the Be2 molecule. In the present study, we report spectroscopic data for Be3 and Be4 obtained via anion photodetachment spectroscopy. The trimer is predicted to have D3h symmetric equilibrium structures for both the neutral molecule and the anion. Photodetachment spectra reveal transitions that originate from the X2A2″ ground state and the 12A1' electronically excited state. The state symmetries were assigned on the basis of anisotropic photoelectron angular distributions. The neutral and anionic forms of Be4 are predicted to be tetrahedral. Franck-Condon diagonal photodetachment was observed with a photoelectron angular distribution consistent with the expected Be4-X2A1 → Be4X1A1 transition. The electron affinities of Be3 and Be4 were determined to be 11363 ± 60 and 13052 ± 50 cm-1, respectively.

Multiple photodetachment of oxygen anions via K -shell excitation and ionization: Direct double-detachment processes and subsequent deexcitation cascades

Experimental cross sections for m-fold photodetachment (m=2-5) of oxygen anions via K-shell excitation and ionization were measured in the photon-energy range of 525-1500 eV using the photon-ion merged-beams technique at a synchrotron light source. The measured cross sections exhibit clear signatures of direct double detachment, including double K-hole creation. The shapes of the double-detachment cross sections as a function of photon energy are in accord with Pattard's [J. Phys. B 35, L207 (2002)] empirical scaling law. We have also followed the complex deexcitation cascades that evolve subsequently to the initial double-detachment events by systematic large-scale cascade calculations. The resulting theoretical product charge-state distributions are in good agreement with the experimental findings.

Dipole effects in the photoelectron angular distributions of the sulfur monoxide anion.

Photoelectron angular distributions (PADs) in SO- photodetachment using linearly polarized 355 nm (3.49 eV), 532 nm (2.33 eV), and 611 nm (2.03 eV) light were investigated via photoelectron imaging spectroscopy. The measurements at 532 and 611 nm access the X3Σ- and a1Δ electronic states of SO, whereas the measurements at 355 nm also access the b1Σ+ state. In aggregate, the photoelectron anisotropy parameter values follow the general trend with respect to electron kinetic energy (eKE) expected for π*-orbital photodetachment. The trend is similar to O2-, but the minimum of the SO- curve is shifted to smaller eKE. This shift is mainly attributed to the exit-channel interactions of the departing electron with the dipole moment of the neutral SO core, rather than the differing shapes of the SO- and O2- molecular orbitals. Of the several ab initio models considered, two approaches yield good agreement with the experiment: one representing the departing electron as a superposition of eigenfunctions of a point dipole-field Hamiltonian, and another describing the outgoing electron in terms of Coulomb waves originating from two separated charge centers, with a partial positive charge on the sulfur and an equal negative charge on the oxygen. These fundamentally related approaches support the conclusion that electron-dipole interactions in the exit channel of SO- photodetachment play an important role in shaping the PADs. While a similar conclusion was previously reached for photodetachment from σ orbitals of CN- (Hart, Lyle, Spellberg, Krylov, Mabbs, J. Phys. Chem. Lett., 2021, 12, 10086-10092), the present work includes the first extension of the dipole-field model to detachment from π* orbitals.

Spectroscopic observation and ultrafast coherent vibrational dynamics of the aqueous phenylalanine radical.

The phenylalanine radical (Phe˙) has been proposed to mediate biological electron transport (ET) and exhibit long-lived electronic coherences following attosecond photoionization. However, the coupling of ultrafast structural reorganization to the oxidation/ionization of biomolecules such as phenylalanine remains unexplored. Moreover, studies of ET involving Phe˙ are hindered by its hitherto unobserved electronic spectrum. Here, we report the spectroscopic observation and coherent vibrational dynamics of aqueous Phe˙, prepared by sub-6 fs photodetachment of phenylalaninate anions. Sub-picosecond transient absorption spectroscopy reveals the ultraviolet absorption signature of Phe˙. Ultrafast structural reorganization drives coherent vibrational motion involving nine fundamental frequencies and one overtone. DFT calculations rationalize the absence of the decarboxylation reaction, a photodegradation pathway previously identified for Phe˙. Our findings guide the interpretation of future attosecond experiments aimed at elucidating coherent electron motion in photoionized aqueous biomolecules and pave way for the spectroscopic identification of Phe˙ in studies of biological ET.

Probing the Exit Channel of the OH + CH3OH → H2O + CH3O Reaction by Photodetachment of CH3O-(H2O).

Transition state dynamics of bimolecular reactions can be probed by photodetachment of a precursor anion when the Franck-Condon region of the corresponding neutral potential energy surface is near a saddle point. In this study, photodetachment of anions at m/z = 49 enabled investigation of the exit channel of the OH + CH3OH → H2O + CH3O reaction using photoelectron-photofragment coincidence spectroscopy. High-level coupled-cluster calculations of the stationary points on the anion surface show that the methoxide-water cluster CH3O-(H2O) is the stable minimum on the anion surface. Photodetachment at a 3.20 eV photon energy leads to long-lived H2O(CH3O) complexes and H2O + CH3O products consistent with both direct dissociative photodetachment and resonance mediated processes on the neutral surface. The partitioning of total kinetic energy in the system indicates that water stretch and bend excitation is induced in dissociative photodetachment and evidence for long-lived complexes consistent with vibrational Feshbach resonances is reported.

Multiple photodetachment of silicon anions via K -shell excitation and ionization

Experimental cross sections for $m$-fold photodetachment ($m=3-6$) of silicon anions via $K$-shell excitation and ionization were measured in the photon-energy range of 1830-1900 eV using the photon-ion merged-beams technique at a synchrotron light source. All cross sections exhibit a threshold behavior that is masked by pre-threshold resonances associated with the excitation of a $1s$ electron to higher, either partly occupied or unoccupied atomic subshells. Results from multi-configuration Dirac-Fock (MCDF) calculations agree with the experimentally derived cross sections for photo-absorption if small energy shifts are applied to the calculated resonance positions and detachment thresholds. Moreover, a systematic approach is applied for modeling the deexcitation cascades that set in after the initial creation of a $K$-shell hole. The resulting product charge-state distributions compare well with the measured ones for direct $K$-shell detachment but less well for resonant $K$-shell excitation. The present results are potentially useful for identifying silicon anions in cold plasmas such as interstellar gas clouds.

Lowest Triplet and Singlet States in N-Methylacridone and N,N'-Dimethylquinacridone: Theory and Experiment.

In this work, radical anion photodetachment photoelectron (PD-PE) spectra of N-methylacridone (NM-AC) and N,N'-dimethyl-trans-quinacridone (NNM-QAC) are presented, from which we derived electron affinities and transition energies from S0 to the lowest excited triplet and singlet states (T1, T2, and S1). Because in molecules with extended π systems and heteroatoms the state density even in the energy range of the lowest excited electronic states is already high, assignment of most of the spectral structures in the PD-PE spectra was possible only on the basis of theoretical calculations. To this end, adiabatic transition energies including zero-point vibrational energy corrections were determined using a combination of density functional theory, time-dependent density functional theory, and multireference configuration interaction methods. Calculated Franck-Condon spectra proved to be particularly valuable for the assignment of the spectra. Surprisingly, the density of electronically excited states in the low-energy regime is smaller for NNM-QAC than for NM-AC. This is due to the fact that the nπ* energies remain nearly the same in the two molecules whereas the lowest ππ* excited singlet and triplet transitions are strongly red-shifted in going from NM-AC to NNM-QAC.

5 YEARS OF ION-LASER INTERACTION MASS SPECTROMETRY—STATUS AND PROSPECTS OF ISOBAR SUPPRESSION IN AMS BY LASERS

ABSTRACTA setup for ion-laser interaction was coupled to the state-of-the-art AMS facility VERA five years ago and its potential and applicability as a new means of isobar suppression in accelerator mass spectrometry (AMS) has since been explored. Laser photodetachment and molecular dissociation processes of anions provide unprecedented isobar suppression factors of >1010 for several established AMS isotopes like 36Cl or 26Al and give access to new AMS isotopes like 90Sr, 135Cs or 182Hf at a 3-MV-tandem facility. Furthermore, Ion-Laser InterAction Mass Spectrometry has been proven to meet AMS requirements regarding reliability and robustness with a typical reproducibility of results of 3%. The benefits of the technique are in principle available to any AMS machine, irrespective of attainable ion beam energy. Since isobar suppression via this technique is so efficient, there often is no need for any additional element separation in the detection setup and selected nuclides may even become accessible without accelerator at all.

Multiple Photodetachment of Carbon Anions via Single and Double Core-Hole Creation.

We report on new measurements of m-fold photodetachment (m=2-5) of carbon anions via K-shell excitation and ionization. The experiments were carried out employing the photon-ion merged-beams technique at a synchrotron light source. While previous measurements were restricted to double detachment (m=2) and to just the lowest-energy K-shell resonance at about 282eV, our absolute experimental m-fold detachment cross sections at photon energies of up to 1000eV exhibit a wealth of new thresholds and resonances. We tentatively identify these features with the aid of detailed atomic-structure calculations. In particular, we find unambiguous evidence for fivefold detachment via double K-hole production.

The ILIAMS project – An RFQ ion beam cooler for selective laser photodetachment at VERA

Selective laser photodetachment of anions is a novel technique for isobar suppression in Accelerator Mass Spectrometry (AMS). Ion-laser interaction times on the order of ms required for near-complete isobar suppression are achieved by retarding the ions in a gas-filled radio frequency quadrupole cooler. Inside this RFQ, the cooled anion beam is overlapped collinearly with an intense cw-laser beam. Within the Ion Laser InterAction Mass Spectrometry (ILIAMS) project at the University of Vienna, a dedicated injector beamline has been coupled to the VERA-AMS facility to explore and develop this method. In this work, experimental investigations on ion beam transmission, stability and elemental selectivity of the new setup are presented.A 532 nm laser at 10 W transmitted power provides suppression factors larger than ten orders of magnitude for S− and MgO− under AMS conditions with simultaneous beam transmission for the ions of interest of up to 80%. The excellent ion identification capabilities of the subsequent AMS system also facilitate the study of destruction and formation of molecular anions inside the ion cooler. These kinetic and chemical reactions with the buffer gas provide additional elemental selectivity in certain cases, whereas others constitute a source of background.

Characterization by laser-induced photodetachment of anions formed during dust particle growth in a magnetically confined very low-pressure argon–acetylene plasma

Anions in low-pressure magnetically confined Ar–C2H2 plasmas were investigated using the laser-induced photodetachment technique. In particular, the influence of the magnetic field (B) was studied. We observed that the density of negatively-charged species n– increases with B and slightly decreases when the C2H2 percentage grows. These phenomena are the result of changes in the plasma kinetics. We also observed that n– decreases as the pressure increases from 2 to 10 mTorr due to the corresponding rise of the collision frequency, which leads to enhanced losses of the negatively-charged species. In parallel, the photodetachment cross-section was deduced from the energy dependence of the photodetachment signal and was found to be close to that of C2H− anions, which indicates that these anions are likely to dominate the negative ion population.

Multi-electron processes in K-shell double and triple photodetachment of oxygen anions

SynopsisAbsolute cross sections for double and triple photodetachment of O− ions have been measured at photon energies around the threshold for K-shell ionization using the photon-ion merged-beams technique at a synchrotron light-source. In addition, corresponding large-scale ab-initio calculations were carried out at a level of complexity that has never been invoked before. From the comparison between experiment and theory it becomes apparent that the inclusion of multi-electron processes such as double shake-up in the theoretical calculations is crucial for the explanation of the experimental findings.

Spin-polarized electrons upon nondipole photodetachment of fullerene anions

SynopsisSpin-polarization of electrons ejected from fullerene anions in the geometry where only nondipole photodetachment effects matter is studied at photon energies of only few tens of eV. The degree of electron spin-polarization is found to be on the order of 5 to 10%, at certain energies. This is remarkable, given that this happens at low photon energies.

Impact of fullerene polarizability on Wigner time delay in photodetachment of fullerene anions

SynopsisThe initial insight into the impact of fullerene polarizability on photodetachment time delay from fullerene anions is exposed. The impact is demonstrated to be significant.

Dynamics of transient species via anion photodetachment.

The dynamics of chemical reactions are often governed by transient species, including the transition state for activated bimolecular reactions. Such transient species are difficult to study experimentally, but it has proven valuable to prepare and probe transition-state dynamics by the photodetachment of anions with an equilibrium geometry similar to the neutral transition state. In this review, recent experimental advances in photoelectron and photoelectron-photofragment coincidence spectroscopy are discussed, as well as the latest progress in the calculation of multidimensional potential energy surfaces and quantum dynamics calculations that have enabled an extension of studies of transition-state dynamics to increasingly multidimensional polyatomic systems. Examples of important dynamical effects such as mode specificity, tunneling, resonance and product energy disposal in reaction dynamics are discussed.

The cryogenic storage ring CSR.

An electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.5 ± 1) K inside the ring, storage time constants of several minutes up to almost an hour were observed for atomic and molecular, anion and cation beams at an energy of 60 keV. The ion-beam intensity, energy-dependent closed-orbit shifts (dispersion), and the focusing properties of the machine were studied by a system of capacitive pickups. The Schottky-noise spectrum of the stored ions revealed a broadening of the momentum distribution on a time scale of 1000 s. Photodetachment of stored anions was used in the beam lifetime measurements. The detachment rate by anion collisions with residual-gas molecules was found to be extremely low. A residual-gas density below 140 cm(-3) is derived, equivalent to a room-temperature pressure below 10(-14) mbar. Fast atomic, molecular, and cluster ion beams stored for long periods of time in a cryogenic environment will allow experiments on collision- and radiation-induced fragmentation processes of ions in known internal quantum states with merged and crossed photon and particle beams.

Full-dimensional characterization of photoelectron spectra of HOCO(-) and DOCO(-) and tunneling facilitated decay of HOCO prepared by anion photodetachment.

The photodetachment of both the HOCO(-) and DOCO(-) anions is investigated using full-dimensional quantum wave packets on new ab initio based global potential energy surfaces for both the neutral and anionic species. The calculated electron affinities and neutral fundamental vibrational frequencies of both isotopomers are in good agreement with available experimental data. The measured photoelectron spectra are also accurately reproduced, further validating the accuracy of the potential energy surfaces. In addition, strong mode specificity is found in the lifetimes of the HOCO vibrational features and the tunneling facilitated predissociation rates to H + CO2 are rationalized using the recently proposed sudden vector projection model.

Laboratory-Frame Photoelectron Angular Distributions in Anion Photodetachment: Insight into Electronic Structure and Intermolecular Interactions

This article provides an overview of some recent advances in the modeling of photoelectron angular distributions in negative-ion photodetachment. Building on the past developments in threshold photodetachment spectroscopy that first tackled the scaling of the partial cross sections with energy, depending on the angular momentum quantum number ℓ, it examines the corresponding formulation of the central potential model and extends it to the more general case of hybrid molecular orbitals. Several conceptual approaches to understanding photoelectron angular distributions are discussed. In one approach, the angular distributions are examined based on the contributions of the symmetry-allowed s and p partial waves of the photodetached electron. In another related approach, the parent molecular orbitals are described based on their dominant s and p characters, whereas the continuum electron is described in terms of interference of the corresponding Δℓ =±1 photodetachment channels.

Spectroscopy of the breaking bond: the diradical intermediate of the ring opening in oxazole

Bond breaking is a challenging problem in both experimental and theoretical chemistry, due to the transient nature and multi-configurational electronic structure of dissociating molecules. We use anion photodetachment to probe the diradical interactions in the ring-opening reaction of oxazole and obtain a self-consistent picture of the breaking bond. Starting from the closed-shell cyclic molecule, the reaction is launched on the anion potential, as an attached electron cleaves a carbon-oxygen bond. In the photodetachment, two neutral potential regions are sampled. One corresponds to a completely dissociated bond, while the other - to the bond fragments separated by approximately 3 Å. At this chemically relevant distance, signatures of lingering through-space interactions between the radical centers are observed.

Photodetachment anisotropy for mixed s-p states: 8/3 and other fractions

An approximate model for analytical prediction of photoelectron angular distributions in anion photodetachment from mixed s-p states is presented. Considering the dipole-allowed s, p, and d free-electron partial waves, the model describes photodetachment anisotropy in terms of the fractional p character of the initial orbital and the A and B coefficients describing the relative intensities of the p → d to p → s and s → p to p → s channels, respectively. The model represents an extension of the central-potential model to an intermediate regime encompassing varying degrees of s and p contributions to the initial bound orbital. This description is applicable to a broad class of hybrid molecular orbitals, particularly those localized predominantly on a single atom. Under the additional assumption of hydrogenic or Slater-type orbitals, the B/A ratio in photodetachment from a mixed 2s-2p state is shown to equal 8/3. Corresponding fractions are derived for other ns-np mixing cases. The predictions of the model are tested on several anion systems, including NH(2)(-) and CCl(2)(-). The quantitative discrepancies in the latter case are attributed to the breakdown of the central-atom approximation and a mechanism for corresponding corrections is indicated.