Novel methodology for systematically constructing global effective models from ab initio-based surfaces: A new insight into high-resolution molecular spectra analysis

In this paper, a novel methodology is presented for the construction of ab initio effective rotation–vibration spectroscopic models from potential energy and dipole moment surfaces. Non-empirical effective Hamiltonians are obtained via the block-diagonalization of selected variationally computed eigenvector matrices. For the first time, the derivation of an effective dipole moment is carried out in a systematic way. This general approach can be implemented quite easily in most of the variational computer codes and turns out to be a clear alternative to the rather involved Van Vleck perturbation method. Symmetry is exploited at all stages to translate first-principles calculations into a set of spectroscopic parameters to be further refined on experiment. We demonstrate on H2CO, PH3, CH4, C2H4, and SF6 that the proposed effective model can provide crucial information to spectroscopists within a very short time compared to empirical spectroscopic models. This approach brings a new insight into high-resolution spectrum analysis of polyatomic molecules and will be also of great help in the modeling of hot atmospheres where completeness is important.