Dissociative Photodetachment Dynamics of the OH-(C2H4) Anion Complex.

Photoelectron-photofragment coincidence (PPC) measurements on OH-(C2H4) anions at a photon energy of 3.20 eV revealed stable and dissociative photodetachment product channels, OH-C2H4 + e- and OH + C2H4 + e-, respectively. The main product channel observed was dissociation to the reactants (>67%), OH + C2H4 (v = 0, 1, 2) + e-, where vibrational excitation in the C-H stretching modes of the C2H4 photofragments corresponds to a minor channel. The low kinetic energy release (KER) of the dissociating fragments is consistent with weak repulsion between the OH + C2H4 reactants near the transition state as well as the partitioning of energy into rotation of the dissociation products. An impulsive model was used to account for rotational energy partitioning in the dissociative photodetachment (DPD) process and showed good agreement with the experimental results. The low KER of the dissociating fragments and the similarities in the photoelectron spectra between stable and dissociative events support a mechanism involving the van der Waals complex formed upon photodetachment of OH-(C2H4) as an intermediate in the dominant OH + C2H4 + e- dissociative channel.

Time-resolved dynamics in iodide-uracil-water clusters upon excitation of the nucleobase.

The dynamics of iodide-uracil-water (I-·U·H2O) clusters following π-π* excitation of the nucleobase are probed using time-resolved photoelectron spectroscopy. Photoexcitation of this cluster at 4.77 eV results in electron transfer from the iodide moiety to the uracil, creating a valence-bound anion within the cross correlation of the pump and probe laser pulses. This species can decay by a number of channels, including autodetachment and dissociation to I- or larger anion fragments. Comparison of the energetics of the photoexcited cluster and its decay dynamics with those of the bare iodide-uracil (I-·U) complex provides a sensitive probe of the effects of microhydration on these species.

Photoelectron-Photofragment Coincidence Spectroscopy With Ions Prepared in a Cryogenic Octopole Accumulation Trap: Collisional Excitation and Buffer Gas Cooling.

A cryogenic octopole accumulation trap (COAT) has been coupled to a photoelectron-photofragment coincidence (PPC) spectrometer allowing for improved control over anion vibrational excitation. The anions are heated and cooled via collisions with buffer gas <17 K. Shorter trapping times (500 µs) prevent thermalization and result in anions with high internal excitation while longer trapping times (80 ms) at cryogenic temperatures thermalize the ions to the temperature of the buffer gas. The capabilities of the COAT are demonstrated using PPC spectroscopy of O 3 - at 388 nm (Ehν = 3.20 eV). Cooling the precursor anions with COAT resulted in the elimination of the autodetachment of vibrationally excited O 2 - produced by the photodissociation O 3 - + hν → O + O 2 - (v ≥ 4). Under heating conditions, a lower limit temperature for the anions was determined to be 1,500 K through Franck-Condon simulations of the photodetachment spectrum of O 3 - , considering a significant fraction of the ions undergo photodissociation in competition with photodetachment. The ability to cool or heat ions by varying ion injection and trapping duration in COAT provides a new flexibility for studying the spectroscopy of cold ions as well as thermally activated processes.

Photoelectron-Photofragment Coincidence Studies on the Dissociation Dynamics of the OH-CH4 Complex.

Photoelectron-photofragment coincidence (PPC) spectroscopy was used to characterize the energetics and dynamics of the OH + CH4 → H2O + CH3 reaction initiated by photodetachment of the OH-(CH4) anion complex. PPC measurements at a photon energy of 3.20 eV yielded stable (OH-CH4 + e-) and dissociative (OH + CH4 (ν1 or ν3, v = 0, 1) + e-) channels. The main channel is dissociation to OH + CH4 + e- with a low kinetic energy release (KER), peaking at 0.04 eV. Interpretation of the experimental results was supported by quantum chemistry and quasiclassical trajectory calculations. The anion potential energy surface was constructed at the correlated coupled cluster singles, doubles, and perturbative triples level with augmented correlation consistent polarized valence triple-ζ basis set, and previously calculated neutral potential energy surfaces were used. Quasiclassical simulation of the dynamics of the OH-CH4 complex was carried out by selecting the momenta and coordinates from the Wigner distribution for the anion, providing the starting point for 4000 trajectories on the neutral potential energy surface. In agreement with the experimental results, most of the trajectories yield slowly recoiling OH + CH4 reactants while some are trapped in the entrance channel van der Waals well.

Resonance-Mediated Below-Threshold Delayed Photoemission and Non-Franck-Condon Photodissociation of Cold Oxyallyl Anions.

The photoexcitation of cold oxyallyl anions was studied below the adiabatic detachment threshold at a photon energy of 1.60 eV. Photodetachment was observed through two product channels, delayed electron emission from a long-lived anionic state and dissociative photodetachment via absorption of a second photon. The former produced stable neutral C3 H4 O, while the latter resulted in the concerted elimination of CO+C2 H4 products. The neutral oxyallyl singlet state has a barrier-free route to cyclopropanone as well as zwitterionic character with a large charge separation and dipole moment. The role of long-lived dipole-bound resonances built on the singlet state below the detachment threshold is discussed. These results provide one of the first observations of delayed photoemission in a small cold molecular radical anion, a consequence of the complex electronic structure of the neutral diradical, and provide an example of resonance-mediated control of the photodissociation processes.

Spectroscopy of Ethylenedione and Ethynediolide: A Reinvestigation.

In an effort to characterize the electronic states of ethylenedione, OCCO, photoelectron-photofragment coincidence (PPC) spectroscopy was applied to measure anions at m/z 56 and 57 using a pulsed discharge of glyoxal vapor and N2 O. PPC measurements at a photon energy of 3.20 eV yield photoelectron spectra in coincidence with either neutral photofragments or stable neutral products. The measurements showed that primarily stable neutral products were formed, with photoelectron spectra consistent with the oxyallyl diradical, C3 H4 O, and acetone enolate radical, C3 H5 O. The spectra were also found to have features nearly identical to those reported for OCCO and HOCCO by Sanov and co-workers. The stability of the neutral products, as well as an examination of spectra reported for the oxyallyl anion and acetone enolate show that the previous assignments of OCCO and HOCCO are in error, and are instead attributed here to the oxyallyl diradical, C3 H4 O, and the acetone enolate radical, C3 H5 O.

Internal energy dependence of the photodissociation dynamics of O3- using cryogenic photoelectron-photofragment coincidence spectroscopy.

Photoelectron-photofragment coincidence (PPC) spectra of ozonide, O3-, were measured at 388 nm (Ehν = 3.20 eV) using a newly constructed cryogenic octopole accumulation trap coupled to a PPC spectrometer. The photoelectron spectra reveal three processes consisting of a stable photodetachment channel, and two distinct photodissociation pathways yielding (1) O2 + O- or (2) O + O2-. The first photodissociation pathway is observed in the PPC spectra by photodetachment of the O- product by a second photon, and produces electronically excited O2(1Δg). The O2- product of the second photodissociation pathway undergoes autodetachment for O2-(2Πg, v″ > 4), a process greatly enhanced by vibrational excitation of the precursor O3-. Cooling anions thermalized at 300 K to <17 K in a cryogenic octopole accumulation trap essentially turns off this autodetachment pathway. The product kinetic energy distribution in coincidence with the autodetached electrons from O2-(v″ = 4) exhibits resolved features consistent with bend (ν2), asymmetric stretch (ν3) and a stretching combination band (ν1 + ν3) in the intermediate electronic state, illustrating the insights that can be gained from kinematically complete measurements. These results are discussed in the context of the low-lying excited states of O3-.