The Microwave Spectrum of m-Tolunitrile: Methyl Internal Rotation and (14)N Nuclear Quadrupole Coupling.

The microwave spectrum of m-tolunitrile (3-methylbenzonitrile, m-C(6)H(4)CH(3)CN) has been investigated in the frequency range from 1 to 4 and 8 to 26.5 GHz. The spectra in the two lowest states of internal methyl rotation (m = 0, +/-1) were recorded by means of pulsed molecular beam Fourier transform microwave (MB-FTMW) spectrometers. The interpretation of the spectra was based on an asymmetric frame-symmetric top Hamiltonian with inclusion of centrifugal distortion terms and first-order contributions from (14)N nuclear quadrupole coupling. A least-squares analysis yielded the rotational constants A = 3295.9103(10) MHz, B = 1199.1188(2) MHz, C = 883.9223(1) MHz, all elements of the nuclear quadrupole coupling tensor chi(aa) = -3.626(1) MHz, chi(bb) = 1.684(1) MHz, chi(cc) = 1.943(1) MHz, and chi(ab) = -1.870(3) MHz, as well as the threefold barrier to internal rotation, V(3) = 14.2 cm(-1), and the angle between the internal rotor axis and the principal moment of inertia a axis, θ = 42.66 degrees, using fixed values for the sixfold barrier term V(6) (-11 cm(-1)) and the moment of inertia of the methyl top I(alpha) (3.16 u Å(2)). Copyright 2000 Academic Press.