Line positions and intensities of the ${\nu}_1$ band of $^{12}$CH$_3$I using mid-infrared optical frequency comb Fourier transform spectroscopy

Abstract

We present a new spectral analysis of the ${\nu}_1$ and ${\nu}_3$+${\nu}_1$-${\nu}_3$ bands of $^{12}$CH$_3$I around 2971 cm$^{-1}$ based on a high-resolution spectrum spanning from 2800 cm$^{-1}$ to 3160 cm$^{-1}$, measured using an optical frequency comb Fourier transform spectrometer. From this spectrum, we previously assigned the ${\nu}_4$ and ${\nu}_3$+${\nu}_4$-${\nu}_3$ bands around 3060 cm$^{-1}$ using PGOPHER, and the line list was incorporated in the HITRAN database. Here, we treat the two fundamental bands, ${\nu}_1$ and ${\nu}_4$, together with the perturbing states, 2${\nu}_2$+${\nu}_3$ and ${\nu}_2$+2${\nu}_6$$^{\pm2}$, as a four-level system connected via Coriolis and Fermi interactions. A similar four-level system is assumed to connect the ${\nu}_3$+${\nu}_1$-${\nu}_3$ and ${\nu}_3$+${\nu}_4$-${\nu}_3$ hot bands, which appear due to the population of the low-lying ${\nu}_3$ state at room temperature, with the 2${\nu}_2$+2${\nu}_3$ and ${\nu}_2$+${\nu}_3$-${\nu}_6$$^{\pm2}$ perturbing states. This treatment provides a good global agreement of the simulated spectra with experiment, and hence accurate line lists and band parameters of the four connected vibrational states in each system. Overall, we assign 4665 transitions in the fundamental band system, with an average error of 0.00071 cm$^{-1}$, a factor of two better than earlier work on the ${\nu}_1$ band using conventional Fourier transform infrared spectroscopy. The ${\nu}_1$ band shows hyperfine splitting, resolvable for transitions with J $\le$ 2 x K. Finally, the spectral intensities of 65 lines of the ${\nu}_1$ band and 7 lines of the ${\nu}_3$+${\nu}_1$-${\nu}_3$ band are reported for the first time using the Voigt line shape as a model in multispectral fitting.