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キーワード:
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要旨:
The analytical, full-dimensional, and global representation of the potential energy
surface of NH3 in the lowest adiabatic electronic state developed previously (Marquardt, R.; et al.
J. Phys. Chem. B 2005, 109, 8439−8451) is improved by adjustment of parameters to an enlarged set of electronic energies from ab initio calculations using the coupled cluster method with single and double substitutions and a perturbative treatment of connected triple excitations (CCSD(T)) and the method of multireference configuration interaction (MRCI). CCSD(T) data were obtained from an extrapolation of aug-cc-pVXZ results to the basis set limit (CBS), as described in a previous work
(Yurchenko, S.N.; et al. J. Chem. Phys 2005, 123, 134308); they cover the region around the NH3 equilibrium structures up to 20 000 hc cm−1. MRCI energies were computed using the aug-cc-pVQZ basis to describe both low lying singlet dissociation channels. Adjustment was performed simultaneously to energies obtained from the different ab initio methods using a merging strategy that includes 10 000 geometries at the CCSD(T) level and 500 geometries at the MRCI level. Characteristic features of this improved representation are NH3 equilibrium geometry req(NH3) ≈ 101.28 pm, αeq(NH3) ≈
107.03°, the inversion barrier at rinv(NH3) ≈ 99.88 pm and 1774 hc cm−1 above the NH3 minimum, and dissociation channel energies 41 051 hc cm−1 (for NH3 → (2B2)NH2 + (2S1/2)H) and 38 450 hc cm−1 (for NH3 → (3Σ−)NH +(1Σg+)H2); the average agreement between calculated and experimental vibrational line positions is 11 cm−1 for 14N1H3 in the spectral region up to 5000 cm−1. A survey of our current knowledge on the vibrational spectroscopy of ammonia and its isotopomers is also given.
