Perturbations Involving nu1 of NCCN.
From high-resolution infrared spectra of 14N12C12C14N, 14N13C13C14N, and 15N12C12C15N, we find that the levels 1000(0)0(0), 1000(0)1(1), 1000(0)2(0,2), and 1000(0)3(1,3) have very pronounced perturbations. Our analysis shows that these perturbations are due to a vibrational resonance among the levels 1000(0)0(0), 0102(0)2(0), and 0102(0)2(2) in the one case, and equivalent levels with one or more additional quanta of nu5 in the other three cases. The resonance constant for the perturbation involving nu1 is 0.25 cm-1. It has the dependence on v5 and l5 that is expected for the sextic potential constant, K124455, although it seems too large for such a high-order constant. The Deltal (or Deltak) = 2 interaction between, for instance, 1000(0)0(0) and 0102(0)2(2e) is shown to be primarily due to the l-type resonance mixing of the 0102(0)2(0) and 0102(0)2(2e) states. The resonance is nearly "turned off" for the 1000(0)2(0,2) and 1000(0)3(1,3) states of 14N13C13C14N because there are no level crossings between the interacting states and the band centers are too far away to have an obvious effect, although careful analysis shows that the perturbation can be seen in their effective centrifugal distortion constants. The spectrum of 15N12C12C15N shows level crossings only in the case of the 1000(0)1(1), 1000(0)2(0,2), and 1000(0)3(1,3) states. Copyright 1999 Academic Press.
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