Millimeter-wave spectroscopy of the chlorine isotopologues of 2-chloropyridine and twenty-three of their vibrationally excited states

Abstract

A combined total of 25 vibrational states of 2-chloropyridine (C5H4NCl, μa = 3.07 D, μb = 1.70 D), including states for both chlorine isotopologues, have been least-squares fit to sextic, A-reduced Hamiltonians with low error (<0.05 MHz). In total, over 22,500 transition frequencies were measured in the 135–375 GHz frequency region. The technique of fixing undeterminable distortion constants to the corresponding values of the ground vibrational state for fundamental states and to extrapolated values for overtone and combination states was employed. The experimentally determined rotational, centrifugal distortion, and vibration-rotation interaction constants are reasonably well-predicted by computational methods (B3LYP/6-311+G(2d,p)). For the chlorine isotopologues, the changes in rotational and quartic distortion constants upon vibrational excitation are quite similar, indicating that it is possible to estimate the constants of a lower-abundance isotopologue’s excited vibrational state using the change in constant observed in the higher-abundance isotopologue. The changes in rotational and quartic distortion constants upon vibrational excitation are also quite similar between analogous vibrational states of 2-chloropyridine and chloropyrazine, despite their differences in molecular composition.