UV frequency metrology on CO (a3P); Isotope effects and sensitivity to a variation of the proton-to-elelctron mass ratio

UV-frequency metrology has been performed on the a{sup 3}{Pi} - X{sup 1}{Sigma}{sup +} (0,0) band of various isotopologues of CO using a frequency-quadrupled injection-seeded narrow-band pulsed titanium:sapphire laser referenced to a frequency comb laser. The band origin is determined with an accuracy of 5 MHz ({delta}{nu}/{nu}=3x10{sup -9}), while the energy differences between rotational levels in the a{sup 3}{Pi} state are determined with an accuracy of 500 kHz. From these measurements, in combination with previously published radio-frequency and microwave data, a set of molecular constants is obtained that describes the level structure of the a{sup 3}{Pi} state of {sup 12}C{sup 16}O and {sup 13}C{sup 16}O with improved accuracy. Transitions in the different isotopologues are well reproduced by scaling the molecular constants of {sup 12}C{sup 16}O via the common mass-scaling rules. Only the value of the band origin could not be scaled, indicative of a breakdown of the Born-Oppenheimer approximation. Our analysis confirms the extreme sensitivity of two-photon microwave transitions between nearly degenerate rotational levels of different {Omega} manifolds for probing a possible variation of the proton-to-electron mass ratio, {mu}=m{sub p}/m{sub e}, on a laboratory time scale.