Rotational spectra of vibrationally excited CCH and CCD.
The millimeter-wave rotational spectra of the lowest bending and stretching vibrational levels of CCH and CCD were observed in a low pressure discharge through acetylene and helium. The rotational, centrifugal distortion, and fine structure constants were determined for the (02(0)0) and (02(2)0) bending states, the (100) and (001) stretching levels, and the (011) combination level of CCH. The same pure bending and stretching levels, and the (110) combination level were observed in CCD. Apparent anomalies in the spectroscopic constants in the bending states were shown to be due to l-type resonances. Hyperfine constants, which in CCH are sensitive to the degree of admixture of the A 2Pi excited electronic state, were determined in the excited vibrational levels of both isotopic species. Theoretical Fermi contact and dipole-dipole hyperfine constants calculated by Peric et al. [J. Mol. Spectrosc. 150, 70 (1991)] were found to be in excellent agreement with the measured constants. In CCD, new rotational lines tentatively assigned to the (100) level largely on the basis of the observed hyperfine structure support the assignment of the C-H stretching fundamental (nu1) by Stephens et al. [J. Mol. Struct. 190, 41 (1988)]. Rotational lines in the excited vibrational levels of CCH are fairly intense in our discharge source because the vibrational excitation temperatures of the bending vibrational levels and the (110) and (011) combination levels are only about 100 K higher than the gas kinetic temperature, unlike the higher frequency stretching vibrations, where the excitation temperatures are five to ten times higher.
Numerical analysis of microwave spectra
Abstract A method is described for identifying the microwave spectrum of a rigid rotor, using only the frequencies of the strongest absorption lines. To that end, parameters related to the rotational constants are varied in steps, and for every step the correspondence between observed and calculated spectrum is checked. The conditions necessary for avoiding the occurrence of too many accidental solutions to the problem are investigated, and an efficient procedure is described. The method has been applied successfully to the identification of a second molecular conformation in the spectrum of fluoroacetic acid.
Optical rotatory dispersion and absolute configuration—III
Abstract Optical rotatory dispersion measurements on pyrrolidine, piperidine, and tetrahydro-isoquinoline alkaloids indicate that the absolute configuration of the α-asymmetric center may be assigned directly from the dispersion curve, provided either that the nitrogen atom is not protonated, or that the compound contains a chromophore absorbing above 200 mμ.