AIMD simulations were conducted with a 1 fs timestep employing a Nosé Thermostat set at 300K. The metal-water interfaces for fcc(111) and hcp(0001) surfaces consisted of 24 water molecules, corresponding to roughly three "layers" of static water. The number of water molecules were scaled down by the relative simulation cell size to 21 on the (100) surfaces and 15 on the (211) surfaces (retaining the same water layer thickness). We benchmarked the water layer thickness against simulations with twice the number of water layers for 11 systems including terrace and step surfaces as shown in the supporting information Tab. S3. We find that the average workfunction during the AIMD trajectory (φ AIMD ) and its polarization and orientation contributions (see below) show almost identical values in agreement with previous work on system size dependence . Cu(111) and Pt(111) are the only exceptions in this regard as they show larger deviation which we attribute to insufficient statistics, however. metal layer which was determined from a radial distribution function . We found that this characteristic distance r