W. Roth et al., The relative stabilities of benzotriazole tautomers determined by a rotational band contour analysis of the N-H stretching vibration, CHEM PHYS, 248(1), 1999, pp. 17-25
The FTIR spectrum of the N-H stretching vibration of 1H- and 2H-benzotriazo
le (BT) has been measured in the gas phase in the region between 3440 cm(-1
) and 3540 cm(-1) at six different temperatures. From the deconvolution of
the partially resolved rotational band contours the contribution of the two
tautomers of BT at each temperature is derived. From this temperature depe
ndency the 1H-tautomer could be determined to be stabilized by 417 cm(-1) (
5 kJ/mol) with respect to the 2H-tautomer. This experimental value is compa
red to results of ab initio calculations on the Hartree-Fock, second order
Moller-Plesset and coupled cluster level of theory as well as to different
density functional methods. It will be pointed out that the correct order o
f energies can only be obtained if electron correlation and zero point ener
gy correction is taken into account in the ab initio calculations. (C) 1999
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