The AE-XA1 System of CaOCH3

We have recorded laser excitation spectra of the CaOCH₃ free radical in a laser ablation molecular beam apparatus, at a spectral resolution of about 0.010 cm⁻¹ and a rotational temperature estimated at 15 K. The two spin-orbit components of the A²E-X²A₁ 0₀⁰ origin band between 625 and 630 nm have been analyzed. Five main subbands were revealed, with ΔK=+1 and K″=0,±1,±2. There was clear evidence of lambda-doubling in the A²E_1/2-X²A₁ 0₀⁰ (F′₁) K′=+1←K″=0 component. A nonlinear least-squares fitting program based on the model developed by Endo et al. [Y. Endo, S. Saito, and E. Hirota, J. Chem. Phys.81, 122-135 (1984)] fit the experimental data (514 A-X lines, N″≤37) with a root mean square deviation of 0.003 cm⁻¹, using known molecular constants of the ground state. The main vibronic (T₀=15 925.1232(5) cm⁻¹), spin-orbit (aζ_ed=66.974 48(51) cm⁻¹), Coriolis (Aζ_t=5.437 30(24)) cm⁻¹, rotational (A=5.439 97(24) cm⁻¹, B=0.117 884(2) cm⁻¹), and fine structure constants (ε₁=−8.208(14)×10⁻³ cm⁻¹, h₁=1.50(12)×10⁻⁴ cm⁻¹, ε_aa=3.58(89)×10⁻³ cm⁻¹, ε_bc=3.20(76)×10⁻³ cm⁻¹) for the excited state have been obtained.