Line Positions and Intensities of the {\nu}$_4$ Band of Methyl Iodide Using Mid-Infrared Optical Frequency Comb Fourier Transform Spectroscopy

TL;DR

This study employs mid-infrared optical frequency comb Fourier transform spectroscopy to precisely measure and assign line positions and intensities of the { u}$_4$ band of methyl iodide, providing new spectral data and analysis.

Contribution

The paper introduces high-resolution spectral measurements of methyl iodide's { u}$_4$ band using a novel comb-based Fourier transform spectrometer, including new line assignments and intensity data.

Findings

2603 transitions assigned to { u}$_4$ band

First report of intensities for 157 transitions

Hyperfine splittings observed for J≤2×K

Abstract

We use optical frequency comb Fourier transform spectroscopy to measure high-resolution spectra of iodomethane, CH$_3$I in the C-H stretch region from 2800 to 3160 cm$^{-1}$. The fast-scanning Fourier transform spectrometer with auto-balanced detection is based on a difference frequency generation comb with repetition rate, f$_{rep}$, of 125 MHz. A series of spectra with sample point spacing equal to f$_{rep}$ are measured at different f$_{rep}$ settings and interleaved to yield sampling point spacing of 11 MHz. Iodomethane is introduced into a 76 m long multipass absorption cell by its vapor pressure at room temperature. The measured spectrum contains three main ro-vibrational features: the parallel vibrational overtone and combination bands centered around 2850 cm$^{-1}$, the symmetric stretch ${\nu}_1$ band centered at 2971 cm$^{-1}$, and the asymmetric stretch ${\nu}_4$ band centered at 3060 cm$^{-1}$. The spectra of the ${\nu}_4$ band and the nearby ${\nu}_3$+${\nu}_4$-${\nu}_3$ hot band are simulated using PGOPHER and a new assignment of these bands is presented. The resolved ro-vibrational structures are used in a least square fit together with the microwave data to provide the upper state parameters. We assign 2603 transitions to the ${\nu}_4$ band with standard deviation (observed - calculated) of 0.00034 cm$^{-1}$, and 831 transitions to the ${\nu}_3$+${\nu}_4$-${\nu}_3$ hot band with standard deviation of 0.00084 cm$^{-1}$. The hyperfine splittings due to the ${^{127}}$I nuclear quadrupole moment are observed for transitions with J$\leq$2xK. Finally, intensities of 157 isolated transitions in the ${\nu}_4$ band are reported for the first time using the Voigt line shape as a model in multispectral fitting.