Spectroscopy of excited states of carbon anions above the photodetachment threshold

Electronic transitions of C3- and C5- to states lying above the electron affinity of the neutral (EA) have been recorded in the gas phase by laser photodetachment spectroscopy. The excited states are identified by comparison with absorption spectra for the mass-selected ions deposited in neon matrices and with ab initio calculations. The C 2 sigma u (+)-X 2 pi g transition and two higher energy band systems are observed for C3-, corresponding to excitation energies more than 1.5 eV above the EA. In the case of C5- the strongest features, at about 0.6 eV above the EA, are attributed to close lying 2 delta g-X 2 pi u and 2 sigma g(-)-X 2 pi u transitions. The dominant configurations in these states identify them as long-lived Feshbach resonances. Lifetimes for these resonances in C3- are estimated to be between 200 fs and 3 ps from the band widths.

Electronic Ground and Excited State Spectroscopy of C(6)H and C(6)D.

Rotational transitions in the X(2)Pi ground state of C(6)H and C(6)D have been measured by Fourier transform microwave and millimeter-wave absorption spectroscopy. More than 150 rotational lines in the ground (2)Pi(3/2) and (2)Pi(1/2) ladders have been observed, allowing an accurate determination of the rotational, fine structure, lambda-doubling, and hyperfine coupling constants using a standard effective Hamiltonian for a molecule in an isolated (2)Pi electronic state. The molecular ground state constants are used to characterize the rotationally resolved origin band of the (2)Pi <-- X(2)Pi electronic transition observed by cavity ring-down laser absorption spectroscopy in a pulsed supersonic slit-jet discharge source. From these data, spectroscopic constants for the excited electronic state are determined. Copyright 1999 Academic Press.