Benzonitrile: Electron affinity, excited states, and anion solvation.

We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X̃(1)A1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile.

Photoelectron angular distributions for states of any mixed character: an experiment-friendly model for atomic, molecular, and cluster anions.

We present a model for laboratory-frame photoelectron angular distributions in direct photodetachment from (in principle) any molecular orbital using linearly polarized light. A transparent mathematical approach is used to generalize the Cooper-Zare central-potential model to anionic states of any mixed character. In the limit of atomic-anion photodetachment, the model reproduces the Cooper-Zare formula.

Low-lying electronic states of cyclopentadienone.

We report a combined experimental and theoretical study of the low-lying electronic states of cyclopentadienone (C5H4O). The cyclopentadienone anion (C5H4O(-)) was generated in the gas phase via reaction of atomic oxygen radical anions (O(-)) with cyclopentanone (C5H8O). Photoelectron imaging was used to gain access to the first three electronic states of C5H4O, including the X (1)A1 ground state and the (3)B2 and (3)A2 excited states.

Photochemistry of fumaronitrile radical anion and its clusters.

The photodetachment and photochemistry of the radical anion of fumaronitrile (trans-1,2-dicyanoethylene) and its clusters are investigated using photoelectron imaging and photofragment spectroscopy. We report the first direct spectroscopic determination of the adiabatic electron affinity (EA) of fumaronitrile (fn) in the gas phase, EA = 1.21 ± 0.

Heterogeneously substituted radicals and carbenes: photoelectron imaging of the FC(H)CN(-) and FCCN(-) anions.

This work represents the next step in the studies of heterogeneous substitution effects in cyanohalo radicals and carbenes. Negative-ion photoelectron imaging was used to investigate the substituted radical and carbene derivatives of fluoroacetonitrile. We report a closed-shell singlet ground state for cyanofluorocarbene, FCCN, with a directly measured adiabatic electron affinity EA = 2.

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.

Heterogeneous substitution effects in chlorocyanomethyl radical and chlorocyanocarbene.

We report a photoelectron-imaging investigation of the chlorocyanomethyl radical (CHClCN) and the corresponding carbene (CClCN). The results are discussed in comparison with the corresponding dichloro- and dicyano-substituted species, focusing on the divergent effects of the halogen and pseudohalogen (CN) substitutions. A cooperative (captodative) interaction of the π-donor Cl and π-acceptor cyano groups favors the increased stability of the CHClCN radical, but a competition of the two substituents is observed in the singlet-triplet splitting of the carbene.

Oxygen cluster anions revisited: solvent-mediated dissociation of the core O4(-) anion.

The electronic structure and photochemistry of the O(2n)(-)(H(2)O)(m), n = 1-6, m = 0-1 cluster anions is investigated at 532 nm using photoelectron imaging and photofragment mass-spectroscopy. The results indicate that both pure oxygen clusters and their hydrated counterparts with n ≥ 2 form an O(4)(-) core. Fragmentation of these clusters yields predominantly O(2)(-) and O(2)(-)·H(2)O anionic products, with the addition of O(4)(-) fragments for larger parent clusters.

O(-) + acetaldehyde reaction products: search for singlet formylmethylene, a Wolff rearrangement intermediate.

The mass-resolved anionic products of the reaction of O(•-) with acetaldehyde, H(3)CCHO, are studied using photoelectron imaging. The primary anionic products are vinoxide, H(2)CCHO(-), formylmethylene anion, HCCHO(•-), and ketenylidene anion, CCO(•-). From photoelectron spectra of HCCHO(•-), the electron affinity of triplet (ground state) formylmethylene (1.

Photodissociation of nitromethane cluster anions.

Three types of anionic fragments are observed in the photodissociation of nitromethane cluster anions, (CH(3)NO(2))(n)(-), n=1-6, at 355 nm: NO(2)(-)(CH(3)NO(2))(k), (CH(3)NO(2))(k)(-), and OH(-) (k View Article and Find Full Text PDF

Photoelectron imaging of NCCCN(-): The triplet ground state and the singlet-triplet splitting of dicyanocarbene.

The photoelectron spectra of NCCCN(-) have been measured at 355 and 266 nm by means of photoelectron imaging. The spectra show two distinct features, corresponding to the ground and first excited states of dycianocarbene. With support from theoretical calculations using the spin-flip coupled-cluster methods, the ground electronic state of HCCCN is assigned as a triplet state, while the first excited state is a closed-shell singlet.

Photoelectron imaging of cyanovinylidene and cyanoacetylene anions.

Negative ions of cyanoacetylene and cyanovinylidene are generated simultaneously via the competing 1,1-H(2)(+) and 1,2-H(2)(+) abstraction channels of O(-) reaction with acrylonitrile. The two stable isomeric forms of the anion, CCHCN(-) and HCCCN(-), are separated by a large (approximately 2 eV) potential energy barrier. Their photodetachment provides access to both the reactant and the product sides of the neutral cyanovinylidene --> cyanoacetylene rearrangement reaction, predicted to involve only a very small barrier.

Laboratory observation of the valence anion of cyanoacetylene, a possible precursor for negative ions in space.

Valence anions of cyanoacetylene, HCCCN(-), are synthesized by the 1,2-H(2) (+) abstraction reaction of O(-) with acrylonitrile, H(2)C=CHCN, while the competing 1,1-H(2) (+) channel of the same reaction yields the cyanovinylidene anions, CCHCN(-). The key to the formation of the elusive, adiabatically weakly bound HCCCN(-) is the bent -C=C-C[triple bond]skeleton of the reactant. The photoelectron spectrum of HCCCN(-), measured by means of photoelectron imaging at 532 nm, consists of a broad structureless band with a vertical detachment energy of 1.