Laser-induced fluorescence excitation and dispersed fluorescence spectroscopy of the Ã(1B1)–(1A1) transition of dichlorocarbene

Abstract

The Ã(¹B₁)–(¹A₁) transition of jet-cooled CCl₂ has been investigated using both laser-induced fluorescence (LIF) excitation and dispersed fluorescence (DF) spectroscopy. DF spectra were taken from over 90 emitting vibronic states over the breadth of the LIF spectrum. 68 ground state vibrational levels were assigned in the C³⁵Cl₂ isotopomer and 47 in C³⁵Cl³⁷Cl. The ground state frequencies were fit to an anharmonic potential yielding: ω^″₁ = 736 cm⁻¹, ω^″₂ = 338 cm⁻¹, ν^″₃ = 760 cm⁻¹, x^″₁₁ = −3.19 cm⁻¹, x^″₂₂ = −0.29 cm⁻¹, x^″₁₂ = −1.80 cm⁻¹, x^″₁₃ = −5.70 cm⁻¹ and x^″₂₃ = −3.80 cm⁻¹. This is the first gas phase measurement of ν^″₃. Despite the close frequency match between ν^″₁ and 2ν^″₂ there was no evidence for Fermi resonance. The intensities of transitions in the DF spectra were analysed to identify the nature of the emitting state. Levels below T₀₀ + 2500 cm⁻¹ in the à state could be assigned simply as combinations and overtones of ν^′₁ and ν^′₂. Between T₀₀ + 2500 and T₀₀ + 5300 cm⁻¹ the emission revealed an increasing mixing between levels within the same polyad, i.e., (m,n,0), (m + 1,n − 2,0), (m + 2,n − 4,0) etc, presumably due to Fermi resonance. This mixing becomes so extensive that simple assignment of the emitting states is not possible. Above T₀₀ + 5300 cm⁻¹ only K′ = 0 states could be identified, indicating that the Renner–Teller intersection between the and à states had been exceeded. This intersection is therefore 22 600 cm⁻¹ above the ground state, in excellent agreement with a previous theoretical calculation of 23 000 cm⁻¹.