Resonances in nitrobenzene probed by the electron attachment to neutral and by the photodetachment from anion.

We probe resonances (transient anions) in nitrobenzene with the focus on the electron emission from these. Experimentally, we populate resonances in two ways: either by the impact of free electrons on the neutral molecule or by the photoexcitation of the bound molecular anion. These two excitation means lead to transient anions in different initial geometries.

The effect of solvation on electron capture revealed using anion two-dimensional photoelectron spectroscopy.

The reaction of low-energy electrons with neutral molecules to form anions plays an important role in chemistry, being involved in, for example, various biological and astrochemical processes. However, key aspects of electron-molecule interactions, such as the effect of incremental solvation on the initially excited electronic resonances, remain poorly understood. Here two-dimensional photoelectron spectroscopy of anionic anthracene and nitrogen-substituted derivatives-solvated by up to five water molecules-reveals that for an incoming electron, resonances red-shift with increasing hydration; but for the anion, the excitation energies of the resonances remain essentially the same.

Mode-Specific Vibrational Autodetachment Following Excitation of Electronic Resonances by Electrons and Photons.

Electronic resonances commonly decay via internal conversion to vibrationally hot anions and subsequent statistical electron emission. We observed vibrational structure in such an emission from the nitrobenzene anion, in both the 2D electron energy loss and 2D photoelectron spectroscopy of the neutral and anion, respectively. The emission peaks could be correlated with calculated nonadiabatic coupling elements for vibrational modes to the electronic continuum from a nonvalence dipole-bound state.

Low energy electron impact resonances of anthracene probed by 2D photoelectron imaging of its radical anion.

Electron-molecule resonances of anthracene were probed by 2D photoelectron imaging of the corresponding radical anion up to 3.7 eV in the continuum. A number of resonances were observed in both the photoelectron spectra and angular distributions, and most resonances showed clear autodetachment dynamics.

Correction: Enhancement of electron accepting ability of para-benzoquinone by a single water molecule.

Correction for 'Enhancement of electron accepting ability of para-benzoquinone by a single water molecule' by Golda Mensa-Bonsu et al., Phys. Chem.

Photoelectron spectroscopy of para-benzoquinone cluster anions.

The photoelectron spectra of para-benzoquinone radical cluster anions, (pBQ) (n = 2-4), taken at hv = 4.00 eV are presented and compared with the photoelectron spectrum of the monomer (n = 1). For all clusters, a direct detachment peak can be identified, and the incremental increase in the vertical detachment energy of ∼0.

Enhancement of electron accepting ability of para-benzoquinone by a single water molecule.

Electron acceptors built upon the para-benzoquinone (pBQ) electrophore are ubiquitous in nature. Here, we present a frequency-resolved photoelectron spectroscopic study of the cold pBQ radical anion, pBQ-, solvated by a single water molecule, as commonly encountered in nature. Our results show that the electron accepting ability is enhanced by the single water molecule and by elevated temperatures.

Photoelectron spectroscopic study of I·ICF: a frontside attack S2 pre-reaction complex.

Photodetachment and 2D photoelectron spectra of the mass-selected I-·CF3I complex are presented together with electronic structure calculations. Calculations show that the I- is located at the iodine side of CF3I. Vertical and adiabatic detachment energies were measured at 4.

Photoexcitation of iodide ion-pyrimidine clusters above the electron detachment threshold: Intracluster electron transfer versus nucleobase-centred excitations.

Laser photodissociation spectroscopy of the I·thymine (I·T) and I·cytosine (I·C) nucleobase clusters has been conducted for the first time across the regions above the electron detachment thresholds to explore the excited states and photodissociation channels. Although photodepletion is strong, only weak ionic photofragment signals are observed, indicating that the clusters decay predominantly by electron detachment. The photodepletion spectra of the I·T and I·C clusters display a prominent dipole-bound excited state (I) in the vicinity of the vertical detachment energy (∼4.