Isotope dependent predissociation in the C1Σ+, v=0 and v=1 states of CO (original) (raw)

2001, The European Physical Journal D

Rotationally resolved spectral lines in the C−X(1, 0) band of carbon monoxide are investigated under high resolution using a coherent vacuum ultraviolet laser source, continuously tunable near 107 nm. Transition frequencies are determined by calibrating against a reference standard of iodine lines, recorded with saturation spectroscopy in the visible range, yielding an absolute accuracy of 0.003 cm −1 in the vacuum ultraviolet. Improved molecular constants for the excited state are derived and no effects of perturbation are found at the present level of accuracy. Line broadening measurements result in information on the excited state lifetime of the C 1 Σ + , v = 1 state for five natural isotopomers of carbon monoxide: τ ( 12 C 17 O) = 280 ps, τ ( 12 C 18 O) = 210 ps, τ ( 13 C 16 O) = 295 ps, τ ( 13 C 17 O) = 160 ps, and τ ( 13 C 18 O) = 150 ps. Within the accuracy of the present measurements no effects of J-dependent lifetimes were observed, for neither of the isotopomers. In addition direct time domain measurements of the lifetime of the C 1 Σ + , v = 0 and v = 1 states of the main isotopomer are performed in a pump-probe experiment using a picosecond VUV-laser, yielding τ ( 12 C 16 O) = 1780 ps for v = 0 and τ ( 12 C 16 O) = 625 ps for v = 1. For C 1 Σ + , v = 0 in 12 C 16 O and 13 C 16 O the same lifetime is found; this lifetime matches experimental values of the oscillator strength and hence supports previous results showing pure radiative decay in this state; the error margins however do not exclude some low level of predissociation. The measurements indicate that the C 1 Σ + , v = 0 state of the 13 C 18 O isotopomer is predissociated with an estimated yield of 17% (i.e. above the level of predissociation for 12 C 16 O.) From the combined data predissociation yields upon excitation of the C 1 Σ + , v = 1 state are derived, lying in the range 0.84-0.91 for the five less abundant isotopomers; for the main 12 C 16 O isotopomer a strongly deviating predissociation yield of 0.65 is deduced.