Simulation of inversion motion and N-H stretching overtone spectra of aniline

A curvilinear internal coordinate Hamiltonian is used to simulate the N-H stretching overtone spectra and the associated inversion splittings in aniline. A simple local mode type model is applied to the N-H stretching and H-N-H bending modes. Geometric algebra is employed to derive the kinetic energy operator for the large amplitude inversion motion. Electronic structure calculations at the Moller-Plesset second order perturbation theory and correlation consistent aug-cc-pVTZ basis set level are used to obtain model parameters, some of which have been optimized with the least-squares method using experimental vibrational term values as data. The observed N-H stretching overtone vibrational levels and the inversional tunneling splittings are well reproduced with our approach. (c) 2007 American Institute of Physics.