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Standard ab initia MO calculations have been carried out by using a modified version of the Gaussion 76 series of programmes [6]. Stationary points on the ground state potential energy surface have been located by using gradient optimization techniques [7] with the 6–31G basis set [8, 9]. More reliable energy comparisons have been obtained by performing single-point calculations at the 6–31G geometries with the polarized 6–31G** basis set [8, 9] and by incorporating valence electron correlation via second-order Møller-Plesset perturbation (MP2) theory [10]. The GRADSCF series of programmes [11] were used to locate the transition structures and the vibrational frequencies, determined at the 6-31G level, in order to characterize the various points as minima (equilibrium structures) or saddle points (transition states) [12], and also to allow the inclusion of the effects of zero-point energies (ZPE) in estimating relative energies. A scaling factor of 0.9 was used for calculating ZPE in order to account for the fact that the normal frequencies are overestimated at the Hartree-Fock level [13].
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The financial support of our work by the Fonds der Chemischen Industrie and the Deutsche Forschungsgemeinschaft is gratefully acknowledged. We are particularly indebted to the Computer Centre of TUB for generously providing computer time.
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Koch, W., Frenking, G. & Schwarz, H. On the barrier and nature of [1.2]-hydrogen migrations in HCN/HNC and their cation radicals. Naturwissenschaften 71, 473–474 (1984). https://doi.org/10.1007/BF00455900
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DOI: https://doi.org/10.1007/BF00455900