Fluorescence Lifetimes of the Ã1Πu State of C3

Abstract

The fluorescence lifetimes of 115 vibrational levels of the Ã1Π(u) state of C3 have been measured under supersonic molecular beam conditions. Of these, ninety-one are Π(u) vibronic levels, for which the lifetimes lie in the range 190-700 ns. The lifetimes of those Π(u) levels where only the bending vibration is excited lie in the range 190-235 ns. There is very little variation with bending quantum number, and the lifetimes of the two orbital components of the 1Π(u) state are essentially the same. When ν1 and ν3 are excited, the lifetimes become longer and/or reach a maximum for levels with v1 + v3 ~ 4. Excitation of the bending vibration in addition to the stretching vibrations shortens the lifetime slightly. Several of the levels show double-exponential decays. Another 23 levels, of Σ(u)+ vibronic symmetry, mostly have lifetimes that are longer than 300 ns. Interaction with nearby "dark" electronic states, such as B1Σ(u)-, B'1Δ(u), C1Π(g), and b3Π(g), is proposed to account for the observed lifetime lengthening. A particularly clear instance of such an interaction is the long lifetime (914 ns) of a perturbing Σ(u)+ level at 30,181 cm(-1), which is confirmed as belonging to the perturbing B'1Δ(u) state. A single level of Δ(u) symmetry at 29,170 cm(-1), which perturbs one of the Π(u) levels, is shown to belong to the à state.