title: The effect of the dipole bound state on AgF⁻ vibrationally resolved photodetachment cross sections and photoelectron angular distributions.
abstract: The first photoelectron spectra of AgF(-) are recorded over the energy range 1.61-1.85 eV using the velocity map imaging technique. The resolved vibrational structure of the AgF X', v' ← AgF(-) X″, v″ = 0 band yields an AgF electron affinity of 1.46 ± 0.01 eV and vibrational frequency of 500 ± 40 cm(-1). For the v' = 2, 3, 4 channels, the photodetachment cross sections and angular distributions undergo rapid changes over a narrow electron kinetic energy range in the region of 50 meV (approximately 13 meV below the opening of the next vibrational channel). This is consistent with Fano-like behavior indicating autodetachment following excitation to a resonant anion state lying in the detachment continuum. EOM-CCSD calculations reveal this to be a dipole bound state. The consistency of the detachment data with the vibrational autodetachment propensity rule Δv = -1 shows that the autodetachment results from breakdown of the Born-Oppenheimer approximation, coupling the vibrational and electronic degrees of freedom.
authors.affiliation: Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis 63130, USA.
authors.forename: Diep Bich
authors.initials: DB
authors.lastname: Dao
authors.affiliation: Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis 63130, USA.
authors.forename: Richard
authors.initials: R
authors.lastname: Mabbs