Erratum: “Dissociative electron attachment to theH2Omolecule. I. Complex-valued potential-energy surfaces for theB1

Three-body breakup in dissociative electron attachment to the water molecule

“…is a resonant process that involves the capture of a free electron into a transient negative ion state which subsequently dissociates to produce neutral and ionic fragments. Previous experimental [1][2][3][4][5][6][7][8][9][10] and theoretical studies [11][12][13][14][15][16][17][18][19] [9] observed the opening of the lower three-body channel, as discerned through the kinetic energy distribution of the O − fragment. However, because of the large O atom/H 2 mass ratio, such a measurement is difficult and a quantitative experimental determination of the final-state branching ratios among the two-and three-body breakup channels has yet to be published.…”

“…We may have overestimated the magnitude of the entrance amplitude (we have calculated the partial width to be 10.30 meV [18]), or overestimated the survival probability. Both probabilities are directly affected by the lifetime of this metastable state as a function of nuclear geometry: a large entrance amplitude implies a small survival probability, and vice-versa.…”

“…We have used our previously calculated [18] complexvalued potential energy surfaces for the three metastable electronic states. As in our previous calculations of the two-body cross sections [19], we used the diabatized 2 A 1 and 2 B 2 surfaces that account for the conical intersection between these states.…”

Observation of the dynamics leading to a conical intersection in dissociative electron attachment to water

“…A conical intersection between the 2 B 2 and 2 A 1 metastable states of the water anion was predicted [24] and demonstrated to be central to the dynamics following attachment to the 2 B 2 state [25,26]. Dissociative electron attachment (DEA) to the H 2 O molecule proceeds via these and the 2 B 1 state at incident electron energies of approximately 12, 8.5 and 6.5 eV respectively, and additionally in the condensed phase via a deep-valence state at approximately 25eV [27].…”

“…In order to make a connection between the lab-frame experimental observations and the dynamics in the body frame, we use a combination of quantum-mechanical cal- culations of the body-frame attachment amplitude [41] and classical trajectory calculations on complex-valued potential energy surfaces [25]. Autoionization on the complex-valued potential energy surfaces is accounted for stochastically via a survival probability at each timestep, exp(−Γ( R)∆t), where Γ( R) is the width of the resonance in the Born-Oppenheimer approximation.…”