Rotational spectrum of a dark state in 2-fluoroethanol using microwave/radio-frequency-infrared multiple resonance

Abstract

Microwave/radio-frequency-infrared multiple resonance has been used with an electric-resonance optothermal spectrometer to characterize a weak 21.6 MHz perturbation in the infrared spectrum of the ν14 C–O stretching vibration of 2-fluoroethanol. The infrared spectrum of 2-fluoroethanol was recorded at a resolution of ∼2 MHz using a tunable microwave-sideband CO2 laser. The spectrum is fit by an asymmetric-rotor Hamiltonian to a precision of 0.6 MHz, except for the transitions to the 413 upper state which are split into doublets by an interaction between the 413 level and a rotational level of a nearby background, or dark, vibrational state. Microwave/radio-frequency-infrared double and triple resonance reveals that the 413 level of the C–O stretching vibration is interacting with the 431 level of the dark state. The rotational constants determined for the dark state allow us to assign the perturbing state to the ν18+4ν21 combination vibration of the lowest energy conformer, where ν18 is the CCO bending vibration and ν21 is the C–C torsional vibration. From the weak ΔKa=2 matrix element between ν14 and ν18+4ν21 it is possible to derive a J=0 anharmonic interaction between these states of ∼3.5 GHz.