Toward Accurate Theoretical Vibrational Spectra: A Case Study for Maleimide

We employ and combine a number of recent developments in vibrational structure methods to push their current size limitations toward molecules with tens of modes and showcase their availability for the maleimide molecule. In particular, we assess the use of different rectilinear vibrational coordinates, namely, normal coordinates, hybrid optimized and localized coordinates, and flexible adaptation of local coordinates of nuclei coordinates. These different coordinate parameterizations are employed in conjunction with the adaptive density-guided approach to generate potential energy surfaces (PESs). A screening procedure is furthermore introduced, which provides estimates of the importance of individual terms in the PES, resulting in significant reductions in the computational cost of the PES construction. We find that all three sets of coordinates provide approximately the same level of accuracy in vibrational structure calculations and report fundamental excitation energies with a mean absolute deviation of less than 12 cm–1 when compared to experimental data. We expect that similar accuracy in vibrational structure calculations can be achieved for molecules of larger size using the proposed procedures.