Observation of a core-excited dipole-bound state $\sim$1 eV above the electron detachment threshold in cryogenically cooled acetylacetonate

TL;DR

This study reports the observation of a core-excited dipole-bound state in cryogenically cooled acetylacetonate anion, revealing a state approximately 1 eV above the electron detachment threshold, using photodetachment spectroscopy.

Contribution

It provides the first experimental evidence of a core-excited dipole-bound state above the detachment threshold in an anion, with detailed spectroscopic characterization.

Findings

Identification of two dipole-bound states in acetylacetonate anion.

Observation of a state 1 eV above the detachment threshold associated with an excited radical state.

Resonant transitions indicating internal conversion processes.

Abstract

Dipole-bound states in anions exist when a polar neutral core binds an electron in a diffuse orbital through charge--dipole interaction. Electronically excited polar neutral cores can also bind an electron in a diffuse orbital to form Core-Excited Dipole-Bound States (CE-DBSs), which are difficult to observe because they usually lie above the electron detachment threshold, leading to very short lifetimes and, thus, unstructured transitions. We report here the photodetachment spectroscopy of cryogenically cooled acetylacetonate anion (C$_5$H$_7$O$_2^-$) recorded by detecting the neutral radical produced upon photodetachment and the infrared spectroscopy in He-nanodroplets. Two DBSs were identified in this anion. One of them lies close to the electron detachment threshold ($\sim$2.74 eV) and is associated with the ground state of the radical (D0-DBS). Surprisingly, the other DBS appears as resonant transitions at 3.69 eV and is assigned to the CE-DBS associated with the first excited state of the radical (D1-DBS). It is proposed that the resonant transitions of the D1-DBS are observed $\sim$1 eV above the detachment threshold because its lifetime is determined by the internal conversion to the D0-DBS, after which the fast electron detachment takes place.