CM04.11.02 : Validating Molecular Dynamics and Joint DFT Predictions of Interfacial Water Using X-Ray Reflectivity

5:00 PM–7:00 PM Apr 5, 2018 (America - Denver)

PCC North, 300 Level, Exhibit Hall C-E

Kendra Letchworth-Weaver1 2 Katherine Harmon3 Alex Gaiduk2 Federico Giberti2 Francois Gygi4 Maria Chan1 Giulia Galli2 1 Paul Fenter1

1, Argonne National Laboratory, Lemont, Illinois, United States
2, The University of Chicago, Chicago, Illinois, United States
3, Northwestern University, Evanston, Illinois, United States
4, University of California, Davis, Davis, California, United States

Capturing the structure and properties of water at the interface with a solid surface presents a unique challenge for both Kohn-Sham and classical density-functional theory due to a complex interplay between chemical binding, electrostatic interactions, steric effects, and dispersion. X-ray reflectivity measurements probe the electron density of aqueous interfaces with high precision, but rely on model-dependent fitting to obtain the corresponding structural model. We present a validation protocol which enables calculation of interfacial X-ray structure factors from theory for direct comparison to experimental measurements. We apply this protocol to benchmark joint DFT, classical molecular dynamics, and first principles molecular dynamics simulations of the Al2O3/water interface, probing the effect of pressure, temperature, and finite size upon the predicted structural model. We explore the relative strengths and weaknesses of each class of theory, gaining insights into the bonding and structural properties of interfacial water which will aid future development of more accurate electronic and classical density-functionals.