The ground state of methane 12CH4 through the forbidden lines of the ν3 band

High resolution spectra of the ν₃ band of methane, ¹²CH₄, were recorded by using a “third generation vacuum Fourier interferometer”; a large pressure range (from 0.009 to 10 Torr) with a sample path fixed at eight meters was used, enabling observation of transitions with intensity ratios as low as $\text{1}\text{10 000}$. More than 350 forbidden transitions of the ν₃ band, including about 125 transitions of the Q⁺ branch, were unambiguously identified. Of the 277 transitions retained for computations, one-hundred have 11 ≤ J ≤ 16. From combination difference relations using pairs of transitions having the same upper state energy level (forbidden-allowed and forbidden-forbidden pairs were used), 276 independent differences between ground state energy levels could be determined with uncertainties of about 0.001 cm^?1.These data yielded the following values for the ground state structure constants of ¹²CH₄ along with their standard deviations (in cm^?1): $\text{β}{}^{\mathrm{o}}\text{hc}\text{=5.2410356±0.0000096}$, $\text{γ}{}^{\mathrm{o}}\text{hc}\text{=(?1±0.00074) 10}{}^{\mathrm{?4}}$, $\text{π}{}^{\mathrm{o}}\text{hc}\text{=(5.78±0.18) 10}{}^{\mathrm{?9}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.4485±0.0023) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.768±0.126) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.602±0.067) 10}{}^{\mathrm{?11}}$, Thus, for the first time, the scalar constant π⁰ has been evaluated and ir values have been obtained for the two tetrahedral constants ?⁰ and ξ⁰; furthermore, these values are in very good agreement with the ones recently determined from radiofrequency data, i.e., in cm^?1: $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.45061±0.00014) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.7634±0.0068) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.5432±0.0040) 10}{}^{\mathrm{?11}}$ From these values, the 276 differences can be reproduced with an overall rms deviation equal to 0.0009 cm^?1.Finally, the ground state energies of ¹²CH₄ have been calculated for J ≤ 16.