For all the pressures explored the interface methanol molecules are undercoordinated with respect to the bulk ones. Our calculation at ambient pressure (0.0001 GPa) reports an average number HB s for bulk methanol molecules of 1.95 in good agreement with previous DFT-MD theoretical works and slightly over esti-Figure . a) Snapshot from DFT-MD simulations of the BLG/methanol system at 0.0001 GPa (with periodic boundary conditions). The oxygen, carbon and hydrogen atoms of the methanol molecules are depicted in red, green and white, respectively. The graphene bonds are coloured in dark grey. b) Time-averaged methanol density profiles normalized with respect to the bulk methanol density. The density is plotted as a function of the distance from the instantaneous BLG surfaces. c) First peaks (L1 and L2) of time-averaged methanol density profiles simulated under different pressure conditions (from 0.0001 to 10 GPa). Each profile is normalized with respect to the corresponding bulk density. d) Radial distribution functions for the carbon inter-layer distances. mated with respect to the experimental value of 1.77. Table . The first column displays the pressure conditions. The second column indicates the number of methanol molecules in the L1 layer. Columns three, four, and five report the total hydrogen bonds, intra-layer hydrogen bonds, and inter-layer hydrogen bonds for methanol molecule, respectively. The final column presents the atomic height distribution of BLG sheets. P(GPa) N mol HB HB intra HB inter S h (Å) 10 -4 (A) 10. 7 Independently on the system pressure, the interface methanol molecules (L1) are found being involved in a strong intralayer H-Bonding (see Table HB intra ) where each methanol molecule (L1) is in average involved in the same number of acceptor and donor intramolecular H-Bonds. The methanol-methanol HB s are found either parallel or perpendicular (pointing the OH toward the liquid phase) with respect to the instantaneous BLG surface. This can be easily appreciated in Fig. where the probability for methanol molecules in the L1 layers to form HBs with a given O-O distance and given orientation with respect to the normal to the BLG layers is reported for all the systems simulated in the 0.0001-10 GPa pressure range. The analysis has been performed on both the upper and lower BLG/methanol interfaces. Our data allows to clearly identify a preferential orientation of the HBs methanol molecules in the L1 layer characterized by their O-H pointed either parallel (cosines ≈ 0) or perpendicular to the methanol bulk phase (cosines <-0.4) Interestingly, the intermolecular O-O HB's distance is found to sensibly decrease only for pressure beyond 2.9 GPa, where the Graphene-methanol distance reaches a plateau at increasing pressure (see L1 peaks positions in Fig. ). For instance, the O-O HB's distances range in the 2.5-2.9 Å interval for pressure<2.9 GPa, while they are found to fluctuate in the 2.5-2.8 Å interval for pressures >2.9 GPa. We also observe a narrowing of the OH-O orientational distribution at high pressure, that indicates a reduction of the OH-O orientational freedom. This is due to the decrease in the methanol-Graphene and methanol L1-L2 distances (see first and second peaks positions in Fig. ) from 0.0001 to 4.9 GPa that limits the OH-O dynamics. The statistical convergence of the distance and orientation probabilities reported in Fig. was assessed by following their evolution every 5 ps of dynamics and verifying their invariance with time. The differences between the upper and lower BLG/methanol interfaces are possibly due to the exploration of different minima, underlying the BLG/methanol interface organization, each one divided by free energy barriers that are difficultly crossed in the picoseconds time scale. Another factor to be considered is the slow dynamics of the C-O libration of interfacial (L1) methanol molecules.