High-resolution Fourier-transform infrared spectroscopy of the ν6 and Coriolis perturbation allowed ν10 modes of ketenimine

Michael K Bane; Evan G Robertson; Christopher D Thompson; Dominique R T Appadoo; Don McNaughton

doi:10.1063/1.3664624

High-resolution Fourier-transform infrared spectroscopy of the ν6 and Coriolis perturbation allowed ν10 modes of ketenimine

J Chem Phys. 2011 Dec 14;135(22):224306. doi: 10.1063/1.3664624.

Authors

Michael K Bane¹, Evan G Robertson, Christopher D Thompson, Dominique R T Appadoo, Don McNaughton

Affiliation

¹ School of Chemistry, Monash University, Wellington Rd., Clayton, Victoria 3800, Australia.

PMID: 22168693
DOI: 10.1063/1.3664624

Abstract

High-resolution FTIR spectra of the short lived species ketenimine have been recorded in the region 700-1300 cm(-1) and over 1500 transitions of the ν(10) and ν(6) modes have been assigned. Effective rotational and centrifugal distortion parameters for the v(10) = 1 and v(6) = 1 (excluding K(a) = 5) states were determined by co-fitting transitions, and treating strong a- and c-axis Coriolis interactions between them. Other perturbations attributed to interactions with the v(8) = 2 and v(12) = 1 + v(8) = 1 dark-states were also observed and treated. The ν(10) transitions are predicted to be inherently very weak, but are enhanced by an intensity stealing effect with the highly IR active ν(6) mode. A mechanism for this intensity stealing in ketenimine is also detailed.