Abstract
The infrared absorption spectrum of the linear C4 radical has been studied in an extension of the original observation of gas-phase C4 by Heath and Saykally [J. Chem. Phys. 94, 3271 (1991)]. The experiment was performed using a flowing mixture of acetylene and helium subjected to a hollow-cathode discharge, which was probed in the 1525–1570 cm−1 spectral region using a tunable diode laser spectrometer. Transitions with N-values up to 60 were measured. Their analysis yielded band origins, rotational, and centrifugal distortion parameters for the lower and upper vibrational states, and l-type doubling parameters for the degenerate bending states ν5 and ν3+ν5. In particular, the ν3 origin was determined to be 1548.6128(4) cm−1, the ground state rotational and centrifugal distortion parameters were B=4979.89(21) MHz and D=0.848(44) kHz, and the l-doubling parameters for ν5 was q5=10.98(13) MHz. This value for q5 was used to estimate the ν5 frequency of gas-phase C4 to be 160±4 cm−1. Both the l=0 and 2 components of the ν3+2ν5−2ν5 sequence band were also tentatively observed, but a detailed analysis was not yet possible. The results were completely consistent with a linear structure for the triplet ground state of C4, and showed no effects of quasilinearity such as that exhibited by C3.
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