Water Dimer under Electric Fields: An Ab Initio Investigation up to Quantum Accuracy

Abstract

It is well-established that strong electric fields (EFs) can align water dipoles, partially order the H-bond network of liquid water, and induce water splitting and proton transfers. To illuminate the fundamental behavior of water under external EFs, we present the first benchmark, to the best of our knowledge, of DFT calculations of the water dimer exposed to intense EFs against coupled cluster calculations. The analyses of the vibrational Stark effect and electron density provide a consistent picture of the intermolecular charge transfer effects driven along the H-bond by the increasing applied field at all theory levels. However, our findings prove that at extreme field regimes (∼1−2 V/Å) DFT calculations significantly exaggerate by ∼10−30% the field-induced strengthening of the H-bond, both within the GGA, hybrid GGA, and hybrid meta-GGA approximations. Notably, a linear correlation emerges between the vibrational Stark effect on OH stretching and H-bond strengthening: a 1 kcal mol −1 increase corresponds to an 80 cm −1 red-shift in OH stretching frequency.