On-the-Fly Ring-Polymer Molecular Dynamics Calculations of the Dissociative Photodetachment Process of the Oxalate Anion

The dissociative photodetachment dynamics of the oxalate anion, C2O4H− + hν → CO2 + HOCO + e−, were theoretically studied using the on-the-fly path-integral and ring-polymer molecular dynamics methods, which can account for nuclear quantum effects at the density-functional theory level in order to compare with the recent experimental study using photoelectron–photofragment coincidence spectroscopy. To reduce computational time, the force acting on each bead of ring-polymer was approximately calculated from the first and second derivatives of the potential energy at the centroid position of the nuclei beads. We find that the calculated photoelectron spectrum qualitatively reproduces the experimental spectrum and that nuclear quantum effects are playing a role in determining spectral widths. The calculated coincidence spectrum is found to reasonably reproduce the experimental spectrum, indicating that a relatively large energy is partitioned into the relative kinetic energy between the CO2 and HOCO fragments. This is because photodetachment of the parent anion leads to Franck–Condon transition to the repulsive region of the neutral potential energy surface. We also find that the dissociation dynamics are slightly different between the two isomers of the C2O4H− anion with closed- and open-form structures.

Dissociative photodetachment of H3O2−: a full-dimensional quantum dynamics study

Good agreement between experimental and theoretical PPC spectra for the pentatomic anion H3O2−.

Theoretical study of the dissociative photodetachment dynamics of the hydrated superoxide anion cluster

The dissociative photodetachment of the hydrated superoxide anion cluster, O2−·H2O + hν → O2 + H2O + e−, is theoretically investigated using path-integral and ring-polymer molecular dynamics simulation methods, which...

Dissociative detachment of the fluoroformate anion

3D fragment imaging of the fluoroformate anion (FCO2−) dissociative photodetachment products shows reductive fragmentation, forming FCO + O, as well as a dominant cleavage of the CF bond.

Dissociative photodetachment dynamics of the oxalate monoanion

Photoelectron–photofragment coincidence spectroscopy is used to investigate the dissociative photodetachment of the oxalate monoanion, which results in HOCO + CO2.

Dissociative photodetachment vs. photodissociation of aromatic carboxylates: the benzoate and naphthoate anions

Photodetachment leads to a stable radical and to dissociation. Both processes are characterized by the kinetic energy release of the neutral particles.

Photoelectron-photofragment coincidence studies of I3− using an electrospray ionization source and a linear accelerator

New insights into the dissociative photodetachment and the charge-symmetric three-body photodissociation of I3− are provided by photoelectron-photofragment coincidence spectroscopy.

Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]−

Photodetaching vibrationally excited FH2O− channels energy into the reaction coordinate of the F + H2O reaction, as shown in this joint experimental-theoretical study.