10.1021/jz200749d.s001 Rogan Carr Rogan Carr Jeffrey Comer Jeffrey Comer Mark D. Ginsberg Mark D. Ginsberg Aleksei Aksimentiev Aleksei Aksimentiev Microscopic Perspective on the Adsorption Isotherm of a Heterogeneous Surface American Chemical Society 2015 surface adsorption Langmuir isotherm fluidic method molecule MD DMMP 2015-12-16 19:31:16 Journal contribution https://acs.figshare.com/articles/journal_contribution/Microscopic_Perspective_on_the_Adsorption_Isotherm_of_a_Heterogeneous_Surface/2016417 Adsorption of dissolved molecules onto solid surfaces can be extremely sensitive to the atomic-scale properties of the solute and surface, causing difficulties for the design of fluidic systems in industrial, medical, and technological applications. In this communication, we show that the Langmuir isotherm for adsorption of a small molecule to a realistic, heterogeneous surface can be predicted from atomic structures of the molecule and surface through molecular dynamics (MD) simulations. We highlight the method by studying the adsorption of dimethyl methylphosphonate (DMMP) to amorphous silica substrates and show that subtle differences in the atomic-scale surface properties can have drastic effects on the Langmuir isotherm. The sensitivity of the method presented is sufficient to permit the optimization of fluidic devices and to determine fundamental design rules for controlling adsorption at the nanoscale.