Rotationally Resolved REMPI Spectra of CaH in a Molecular Beam

Rotationally resolved spectra of the CaH radical using a supersonic molecular beam are reported. Thus, high energy resolution of the (1+1′) REMPI spectra corresponding to the A←X and B←X electronic transitions were measured which allowed for the first time a clear and precise analysis of the low rotational part (J≤7) of the CaH spectrum. A comparison with previous studies revealed that the commonly accepted energy separation between the two band heads of B−X (v′=1, v′=0) of 10 cm⁻¹ is not correct. A value of ca. 1.6 cm⁻¹ was found to be more realistic. On the other hand, the present study confirmed that the perturbation appears only for v′=1, N′>3 of the B state.