New Ab Initio Potential Energy Surfaces for NH3 Constructed from Explicitly Correlated Coupled-Cluster Methods

Accurate calculation of ab initio potential energy surfaces (PESs) for the NH3 molecule is a difficult task because of the poor convergence of the standard CCSD­(T) method with respect to the basis size. Currently, the best available NH3 PESs contain empirically refined parameters. In this paper, we show that CCSD­(T)/aug-cc-pCV6Z calculations are not sufficient to properly describe the PES over a large range of nuclear configurations. However, the PES obtained by the extrapolation of the CCSD­(T)/aug-cc-pCVXZ (X = T, Q, 5, and 6) energies to the complete basis set limit is closer to that based on the explicitly correlated CCSD­(T)-F12a method using the cc-pCVQZ-F12 orbital basis set. All of the ab initio PESs constructed in this work include the following corrections: one electron relativistic effects, diagonal Born–Oppenheimer correction, and high-order electronic correlations (CCSDT, CCSDTQ, and CCSDTQP). Finally, the root-mean-square deviation between the predicted band centers obtained from our final “pure” ab initio PES and the experimental ones in the spectral region [0–7000] cm–1 is divided by two compared to the most accurate ab initio PES available in the literature.