A Simple Additive Potential Model for Simulating Hydrogen Peroxide in Chemical and Biological Systems.

Hydrogen peroxide (H2O2) has numerous industrial, environmental, medical, cosmetic, and biological applications. Given its importance, we provide a simple model as an alternative to experiment for studying the properties of pure liquid H2O2 and its concentrated aqueous solutions, which are hazardous, and for understanding the biological roles of H2O2 at the molecular level. A four-site additive model is calibrated for H2O2 based on the ab initio and experimental properties of the gaseous monomer and the density and heat of vaporization of liquid H2O2 at 0 °C. Our model together with the TIP3P water model reproduce the ab initio binding energies of (H2O2) m, H2O2· nH2O, and nH2O2·H2O clusters ( m = 2, 3 and n = 1, 2) calculated at the MP2 level using the 6-311++G(d,p) or the 6-311++G(3df,3pd) basis set. It yields structure, the self-diffusion coefficient, heat capacity, and densities at temperatures up to 200 °C of the pure liquid in good agreement with experiment. The model correctly predicts the hydration free energy of H2O2 and reproduces the experimental density of aqueous H2O2 solutions at 0-96 °C. Investigation of the solvation of H2O2 and H2O in aqueous H2O2 solutions reveals that, as in the gas phase, H2O2 is a better H-bond donor but poorer acceptor than H2O and the bonding stability follows the order Op-Hp···Ow > Ow-Hw···Ow ≥ Op-Hp···Op > Ow-Hw···Op. Stronger H-bonding in H2O/H2O2 mixtures than in the pure liquids is consistent with exothermic heats of mixing and explains why the observed density and vapor pressure of the aqueous solutions are higher and lower, respectively, than expected from ideal mixing. Results also show that H2O2 adopts a skewed equilibrium geometry in gas and liquid phases but more polar cis and nonpolar trans conformations also are accessible and will stabilize H2O2 in environments of different polarity. In sum, our simple model presents a reliable tool for simulating H2O2 in chemistry and biology.