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magnitude shorter than those of benzene and its alkyl derivatives. The relatively short radiative lifetimes of the lowest triplet states, as well as the enhanced phosphorescence-to-fluorescence quantum-yield ratios 5 ,14 of aromatic amines (relative to hydrocarbon analogs), can be taken as a manifestation of enhanced spin-orbit coupling resulting from the presence of the lone-pair orbitals in these molecules. The lack of a significant deuterium effect in the phosphorescence mean lifetime 14 V. Ermolaev, Opt. Spectry. (USSR) 11, 266 (1961) [Opt. i Spektroskopiya 11, 492 (196l)J. of aniline also reflects the relative unimportance of the radiationless transitions from the lowest triplet state of this molecule.The results summarized in this present paper therefore indicate that the l~a1r CT transitions play an important role in spin-orbit coupling of aromatic amines. ACKNOWLEDGMENTSWe wish to thank Professor A. C. Albrecht for many helpful comments and J. Schmieg and C. Lazzara for their assistance with the manuscript.The microwave spectra of methylthiocyanate, methylisocyanate, and methylisothiocyanate have been re-examined under high resolution. The rotational constants of methylthiocyanate are A = 15 703.0±2.0 MHz, B=4155.59±0.1 MHz, and C=3354.16±0.1 MHz. The barrier to internal rotation of the methyl group determined from the Q-branch splittings in the v=O torsional state is 1600±80 cal/mole. Analysis of the UN quadrupole splitting yields the following coupling constants: xaa=-3.13±0.05 MHz, Xbb=2.19± 0.05 MHz, Xcc=0.94±0.05 MHz. The barrier to internal rotation in methylisocyanate is found to be 83±15 cal/mole from the splitting of the K =0, m= ±3 lines, and Xa. is 2.86±0.03 MHz. The corresponding parameters in methylisothiocyanate are found to be 304±50 caI/mole and 1.90±0.03 MHz. The microwave data are consistent with a CNC angle of 147°-148° in methylisothiocyanate as opposed to 140° in methylisocyanate and indicates C-N bond lengths in these compounds of 1.43-1.45 A. The observed spectra of methylisocyanate and methylisothiocyanate cannot be fit by the usual semirigid internal-rotation treatment. A reasonable fit of the K = 0 lines is obtained only if a semiempirical nonrigid correction factor of the form CT11I 2 is used and, in addition, the methyl symmetry axis is tilted ,.....,3° toward the lone-pair electrons on the nitrogen atom. Calculations based on a model which includes the effects of the CNC bending motion on the over-all and internal rotation failed to improve the fit. It is concluded that an extensive vibrationrotation-interaction treatment is necessary in order to achieve a quantitative fit of the microwave data. A normal-coordinate analysis of the three molecules studied was carried out using a valence force field. The present vibrational assignment in methylthiocyanate is substantiated, and the lowest-frequency mode is found to contain a large contribution from the S-C=N bend in addition to the CSC bend. The lowestfrequency modes in methylisocyanate and methylisothiocyanate are likewise n...

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