INFRARED-SPECTRA OF PERDEUTERATED NAPHTHALENE, PHENANTHRENE, CHRYSENE, AND PYRENE

Citation
Cw. Bauschlicher et al., INFRARED-SPECTRA OF PERDEUTERATED NAPHTHALENE, PHENANTHRENE, CHRYSENE, AND PYRENE, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(13), 1997, pp. 2414-2422
Citations number
26
Categorie Soggetti
Chemistry Physical
ISSN journal
10895639
Volume
101
Issue
13
Year of publication
1997
Pages
2414 - 2422
Database
ISI
SICI code
1089-5639(1997)101:13<2414:IOPNPC>2.0.ZU;2-Q
Abstract
Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of perdeuterated na phthalene, phenanthrene, pyrene, and chrysene. We also report matrix-i solation spectra for these four species. The theoretical and experimen tal frequencies and relative intensities for the perdeuterated species are in generally good agreement. The effect of perdeuteration is to r educe the sum of the integrated intensities by a factor of about 1.75. This reduction occurs for all vibrational motions, except for the wea k low-frequency ring deformation modes. There is also a significant re distribution 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 theo retical isotopic ratios provide an excellent diagnostic of the degree of C-H(C-D) involvement in the vibrational bands, allowing in most cas es a clear distinction of the type of motion.