We report on a form of gas-phase anion action spectroscopy based on infrared multiple photon electron detachment and subsequent capture of the free electrons by a neutral electron scavenger in a Fourier Transform Ion Cyclotron Resonance (FTICR) mass spectrometer. This method allows one to obtain background-free spectra of strongly bound anions, for which no dissociation channels are observed. The first gas-phase spectra of acetate and propionate are presented using SF6 as electron scavenger and a free electron laser as source of intense and tunable infrared radiation. To validate the method, we compare infrared spectra obtained through multiple photon electron detachment/attachment and multiple photon dissociation for the benzoate anion. In addition, different electron acceptors are used, comparing both associative and dissociative electron capture. The relative energies of dissociation (by CO2 loss) and electron detachment are investigated for all three anions by DFT and CCSD(T) methods. DFT calculations are also employed to predict vibrational frequencies, which provide a good fit to the infrared spectra observed. The frequencies of the symmetric and antisymmetric carboxylate stretching modes for the aliphatic carboxylates are compared to those previously observed in condensed-phase IR spectra and to those reported for gas-phase benzoate, showing a strong influence of the solution environment and a slight substituent effect on the antisymmetric stretch.
Associative electronic detachment (AED) between anions and neutral atoms leads to the detachment of the anion's electron resulting in the formation of a neutral molecule. It plays a key role in chemical reaction networks, like the interstellar medium, the Earth's ionosphere and biochemical processes. Here, a class of AED involving a closed-shell anion (OH^-) and alkali atoms (rubidium) is investigated by precisely controlling the fraction of electronically excited rubidium. Reaction with the ground state atom gives rise to a stable intermediate complex with an electron solely bound via dipolar…
Photodetachment spectroscopy of OH- and H3O2- anions has been performed in a cryogenic 22-pole radiofrequency multipole trap. Measurements of the detachment cross section as a function of laser frequency near threshold have been analysed. Using this bound-free spectroscopy approach we could demonstrate rotational and vibrational cooling of the trapped anions by the buffer gas in the multipole trap. Below 50 K the OH- rotational temperature shows deviations from the buffer gas temperature, and possible causes for this are discussed. For H3O2- vibrational cooling of the lowest vibrational quantu…
Birch reduction is a time-proven way to hydrogenate aromatic hydrocarbons (such as benzene), which relies on the reducing power of electrons released from alkali metals into liquid ammonia. We have succeeded to characterize the key intermediates of the Birch reduction process - the solvated electron and dielectron and the benzene radical anion - using cyclic voltammetry and photoelectron spectroscopy, aided by electronic structure calculations. In this way, we not only quantify the electron binding energies of these species, which are decisive for the mechanism of the reaction but also use Bir…
We present a theoretical investigation of the hydrated hydroxide anion clusters OH(H$_{2}$O)$_{n}^{-}$ and of the collisional complexes H-OH(H$_{2}$O)$_{n}^{-}$ and Rb-OH(H$_{2}$O)$_{n}^{-}$ (with n$=1-4$). The MP2 and CCSD(T) methods are used to calculate interaction energies, optimized geometries and vertical detachment energies. Part of the potential energy surfaces are explored with a focus on the autodetachment region. We point out the importance of diffuse functions to correctly describe the latter. We use our results to discuss the different water loss and electronic detachment channels…
Photoelectron circular dichroism in the one-photon detachment of a model methane-like chiral anionic system is studied theoretically by the single center method. The computed chiral asymmetry, characterized by the dichroic parameter $β_1$ of up to about $\pm3\%$, is in a qualitative agreement with very recent experimental observations on photodetachment in amino acid anions [P. Krüger and K.-M. Weitzel, Angew. Chem. Int. Ed. 60, 17861 (2021)]. Our findings confirm a general assumption that the magnitude of PECD is governed by the ability of an outgoing photoelectron wave packet to accumulate c…
Photodetachment thermometry on a beam of OH$^-$ in a cryogenic storage ring cooled to below 10 K is carried out using two-dimensional, frequency and time dependent photodetachment spectroscopy over 20 minutes of ion storage. In equilibrium with the low-level blackbody field, we find an effective radiative temperature near 15 K with about 90% of all ions in the rotational ground state. We measure the J = 1 natural lifetime (about 193 s) and determine the OH$^-$ rotational transition dipole moment with 1.5% uncertainty. We also measure rotationally dependent relative near-threshold photodetachme…
Time resolved transient absorption spectroscopy has been used to determine quantum yields for electron photodetachment in 193 nm and (where possible) 248 nm laser excitation of miscellaneous aqueous anions, including hexacyanoferrate(II), sulfate, sulfite, halide anions (Cl-, Br-, and I-), pseudohalide anions (OH-, HS-, CNS-), and several common inorganic anions for which no quantum yields have been reported heretofore: SO3=, NO2-, NO3-, ClO3- and ClO4-. Molar extinction coefficients for these anions and photoproducts of electron detachment from these anions at the excitation wavelengths were …
In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as extreme halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-molecule problem using a non-adiab…
In concentrated solutions of NaClO4 and Na2SO4, the quantum yield for free electron generated by detachment from photoexcited anions (such as I-, OH-, ClO^4-, and [SO3]^2-) linearly decreases by 6-12% per 1 M ionic strength. In 9 M sodium perchlorate solution, this quantum yield decreases by roughly an order of magnitude. Ultrafast kinetic studies of 200 nm photon induced electron detachment from Br-, HO- and [SO3]^2- suggest that the prompt yield of thermalized electron does not change in these solutions; rather, the ionic strength effect originates in more efficient recombination of geminate…
Photostimulated electron detachment from aqueous inorganic anions is the simplest example of solvent-mediated electron transfer. Here we contrast the behavior of halide anions with that of small polyatomic anions, such as pseudohalide anions (e.g., HS-) and common polyvalent anions (e.g., SO32-). Geminate recombination dynamics of hydrated electrons generated by 200 nm photoexcitation of aqueous anions (I-, Br-, OH-, HS-, CNS-, CO32-, SO32-, and Fe(CN)64-) have been studied. Prompt quantum yields for the formation of solvated, thermalized electrons and quantum yields for free electrons were de…
Spectroscopy of deprotonated anions of cold chlorophyll pigments, an approach to their photosynthetic properties
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d'Orsay (ISMO)（巴黎萨克雷大学，法国国家科学研究中心，奥赛分子科学研究所）；Université Paris-Saclay, CEA, CNRS, Institute for Integrative Biology of the Cell (I2BC)（巴黎萨克雷大学，法国原子能和替代能源委员会，法国国家科学研究中心，细胞整合生物学研究所）
The direct dynamical paths leading to Associative Detachment (AD) in the gas-phase, and specifically in the low-temperature regions of the Dark Molecular Clouds (DMC) in the ISM, or in cold trap laboratory experiments, are investigated with quantum chemical methods by using a high-level multi-reference Configuration Interaction (CI) approach that employs single and double excitations plus Davidson perturbative correction [MRSDCI(Q)] and the d-aug-cc-pV5Z basis set. The potential energy curves for H + CN- are constructed for different directions of the H partner approaching the CN- anion within…
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…
Time-resolved x-ray absorption spectroscopy monitors the transient species generated by one-photon detachment of an electron from aqueous bromide. Hydrated bromine atoms with a lifetime of ca. 17 ns were observed, nearly half of which react with excess Br- to form Br2-. The K-edge spectra of the Br atom and Br2- anion exhibit distinctive resonant transitions that are absent for the Br- precursor. The absorption spectra indicate that the solvent shell around a Br0 atom is defined primarily by hydrophobic interactions, in agreement with a Monte Carlo simulation of the solvent structure.
