Discovery of New Lines in the R9 Multiplet of the 2v_{3} Band of ^{12}CH_{4}

We present the first results for resolving methane (CH_{4}) line transition frequencies down to the kilohertz level for overlapping lines using comb-linked cavity ring-down spectroscopy, while most available laboratory measurements, having resolution at the megahertz level, cannot separate merged lines. To demonstrate the technique, Lamb-dip spectra and linear-absorption spectra were used to identify overlapped lines of vibration-rotation spectra in the R9 multiplet of the 2v_{3} band. Three new weak lines were found for the first time. The experimental methods are extensible to other important bands of CH_{4} and many other gas-phase molecules, and should provide a more detailed understanding of molecular structure and line parameters for future high-precision studies.