Dissociation energies of the I(3/2g) and I(1/2g) states of Ar⁺₂

Abstract

Rotationally resolved pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectra of ⁴⁰Ar₂ and ³⁶Ar₂ have been recorded between 124650cm⁻¹ and 127 150cm⁻¹ following resonant two-photon excitation via the 0⁺ _u (v¹= 0) Rydberg state located below the Ar (¹S₀) + Ar∗((3p)⁵4s′ [1/2]₁) dissociation limit. Four overlapping vibrational progressions were observed and attributed to transitions to the I(1/2u) u⁺ = 35–50, I(3/2g) u⁺ = 0–10, I(1/2g) v⁺ = 0–6 and I(3/2u) v⁺ = 0–2 vibronic states of Ar⁺ ₂. The vibrational quantum numbers of the ionic states were derived from an analysis of the isotopic shifts, and the dissociation energies of the I(3/2g) (D⁺ ₀(⁴⁰Ar⁺ ₂:) = 1509.4 ± 1.2cm⁻¹) and the I(1/2g) (D⁺ ₀(⁴⁰Ar⁺ ₂) = 616.3 ± 1.2cm⁻¹) states were determined.