Accurate vibrational hydrogen-bond shift predictions with multicomponent DFT

Abstract

In this work we explore the use of multicomponent methods for the computational simulation of anharmonic OH vibrational shifts. Multicomponent methodologies have become popular over the last years, but still are limited in their application range. However, by enabling the simultaneous quantum treatment of protonic and electronic wave functions/densities, they hold promise for the treatment of anharmonic effects and proton vibrations in general. This potential has only been probed but not fully realized so far. This study investigates the performance of Nuclear-Electronic Orbital Density Functional Theory (NEO-DFT) in the prediction of water OH shifts upon complexation with organic molecules. We make use of the HyDRA database, expanded to 35 hydrogen-bonded monohydrates of small organic molecules, and evaluate a range of DFT functionals, both hybrid and double-hybrid. We introduce a robust prediction strategy based on common ingredients available when running conventional DFT and NEO-DFT calculations, which for the first time reduces the root mean square deviation (RMSD) values below 10 cm⁻¹ for the set. Double-hybrid functionals in combination with a DFT treatment of the proton of interest is found to be particularly promising. The new systems added to the HyDRA dataset are presented and used as an extra test to the methodology.