The general understanding of so-called electrochemical Stark tuning rates, that is, the potential dependence of vibrational frequency of CO adsorbed on Pt(1 1 1), has developed over the past thirty years in terms of two semiempirical models. The first is the Fermi level shift model used in non-self-consistent-field one-electron molecular orbital theory. This approach has provided qualitative understanding in terms of Fermi level-dependent variations in sigma and pi orbital bonding between CO and the electrode surface atoms. The second is the use of self-consistent-field theory with surface charging to create adjustable electric fields. Adsorbed CO then reacts to the field in a classical Stark effect with some small uncharacterized Fermi level shift superimposed. It is now possible, using two-dimensional density functional theory, including electrolyte polarization from surface charging, and the dielectric continuum to approximate salvation energy, to calculate the tuning rate in response to shifts in the Fermi level and electrode potential caused by changing the surface charge density. Here we apply this first principles method to calculate trends in the tuning rate for CO adsorbed on 1-fold Pt(1 1 1) sites with changes in CO(ads) coverage and with changes in electrolyte pH. The tuning rate is calculated to decrease as the coverage is increased and, for high coverage, to increase as the pH is increased. These trends are shown to be in qualitative agreement with the very little existing experimental data for these trends. (C) 2013 Elsevier Ltd. All rights reserved.