THE $\upsilon_{13}$ FUNDAMENTAL BAND OF BENZENE

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1982

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Ohio State University

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The perpendicular band of the E1u vibration υ13 of benzene, occurring near 6.7μm, has been measured on a BOMEM high-resolution Fourier transform spectrometer with a 246 cm optical path difference. The observed line width (full width at half height) of −0.0048cm−1 was reduced by deconvolution to −0.0020cm−1, which is slightly below the Doppler limit. The dense rotational structure was well resolved, and it was possible to assign over 120 subbands in the region 1466−1504cm−1. A perturbation, identified as a third-order Jx,y-Coriolis interaction with a state (presumably the A2u component of υ4+2υ20) located only −0.055cm−1 above the fundamental, causes distortion of the rotational structure and formation of subband heads in the low-k PQ-branches, which exhibit a striking line-like shape, The spectrum was analyzed in detail with the aid of the computer program SYMTOP for the treatment of symmetric top bands whose upper states are involved in arbitrary interactions. Some of the spectroscopic constants obtained for the υ13 state are υo=1483.9852cm−1;αu=B′−B0=−6.36×10−5cm−1;αC=C′−C0=−9.40×10−5cm−1;Cζ=−2.671×10−2cm−1q=−2.95×10−4cm−1, the over-all standard deviation of the fit was 0.0005cm−1.

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