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Infrared Spectra of Perdeuterated Naphthalene, Phenanthrene, Chrysene, and Pyrene

1997; American Chemical Society; Volume: 101; Issue: 13 Linguagem: Inglês

10.1021/jp963740w

1520-5215

Charles W. Bauschlicher, Stephen R. Langhoff, Scott A. Sandford, Douglas M. Hudgins,

Molecular Spectroscopy and Structure

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of perdeuterated naphthalene, phenanthrene, pyrene, and chrysene. We also report matrix-isolation spectra for these four species. The theoretical and experimental frequencies and relative intensities for the perdeuterated species are in generally good agreement. The effect of perdeuteration is to reduce the sum of the integrated intensities by a factor of about 1.75. This reduction occurs for all vibrational motions, except for the weak low-frequency ring deformation modes. There is also a significant redistribution of the relative intensities between the out-of-plane C−D bands relative to those found for the out-of-plane C−H bands. The theoretical isotopic ratios provide an excellent diagnostic of the degree of C−H(C−D) involvement in the vibrational bands, allowing in most cases a clear distinction of the type of motion.