Investigation of the Second Harmonic Generation at the Water–Vacuum Interface by Using Multi‐Scale Modeling Methods

The Sequential Quantum Mechanics/Molecular Mechanics scheme has been enacted to perform a systematic investigation of the polarizability (α) and first hyperpolarizability (β) responses at the water–vacuum interface. After performing classical molecular dynamics simulations to provide snapshots of the structures, quantum chemistry calculations of the linear and nonlinear optical responses have been performed for clusters of five water molecules at the time‐dependent DFT level in combination with different embedding schemes, ranging from point charges to polarizable point charges, with and without local field effects. When going from the bulk to the interface, the main observations of these calculations encompass i) a modest increase of the average polarizability but an increase by about a factor of two of its anisotropy, ii) an increase by about 20 % of the β(HRS) response, accompanied by a small increase of its depolarization ratio, and iii) a net increase of the component of the β tensor normal to the interface (β(zzz) ) as well as of β ( // ). Globally, the interfacial effects on β are localized at the first molecular layer while they are observed up to the fourth molecular layer on α.