Nitric oxide, NO, is a free radical that forms dimers, (NO)2, at its vapor–liquid coexisting temperatures. In this work, we developed an all-atom force field for NO and (NO)2. To assess the performance of this force field, we computed the vapor–liquid equilibrium (VLE) properties of the reactive NO–(NO)2 system, as well as those of pure NO and pure (NO)2, using Continuous Fractional Component Monte Carlo (CFCMC) simulations. We then compared the results with the available experimental data and predictions from two previously developed force fields. For the reactive NO–(NO)2 system, we performed CFCMC simulations in the reactive Gibbs ensemble in which the formation of NO dimers, 2NO ⇌ (NO)2, is considered. The predicted coexistence vapor–liquid densities, dimer mole fractions in the liquid phase, saturated vapor pressures, and heats of vaporization using our force field in the temperature range 120 K to 170 K are in excellent agreement with experimental values. In addition, we conducted a systematic parameter study to analyze the sensitivity of the new force field parameters and the isolated molecule partition functions of (NO)2 on the VLE properties of the reactive NO–(NO)2 system. The results indicate that the VLE properties of the reactive NO–(NO)2 system are affected by both the force field parameters of the involved species as well as the isolated molecule partition functions of (NO)2.

Hydrogen peroxide plays a key role in many environmental and industrial chemical processes. We performed classical Molecular Dynamics and Continuous Fractional Component Monte Carlo simulations to calculate thermodynamic properties of H₂O₂ in aqueous solutions. The quality of the available force fields for H₂O₂ developed by Orabi and English (2018) [67], and by Cordeiro (2014) [69] was systematically evaluated. To assess which water force field is suitable for predicting properties of H₂O₂ in aqueous solutions, four widely used water force fields were used, namely the TIP3P, TIP4P/2005, TIP5P-E, and a modified TIP3P force field. While the computed densities of pure H₂O₂ in the temperature range of 253 - 353 K using the force field by Orabi & English are in excellent agreement with experimental results, the densities using the force field by Cordeiro are underestimated by 3%. The TIP4P/2005 force field in combination with the H₂O₂ force field developed by Orabi & English can predict the densities of H₂O₂ aqueous solution for the whole range of H₂O₂ mole fractions in very good agreement with experimental results. The TIP4P/2005 force field in combination with either of the H₂O₂ force fields can predict the viscosities of H₂O₂ aqueous solutions for the whole range of H₂O₂ mole fractions in reasonably good agreement with experimental results. The computed diffusion coefficients for H₂O₂ and water molecules using the TIP4P/2005 force field with either of the H₂O₂ force fields are almost constant for the whole range of H₂O₂ mole fractions. Hydrogen bond analysis showed a steady increase in the number of hydrogen bonds with the solute concentrations in H₂O₂ aqueous solutions for all combinations except for the Cordeiro-TIP5P-E and Orabi-TIP5P-E systems, which showed a minimum at intermediate concentrations. The Cordeiro force field for H₂O₂ in combination with either of the water force fields can predict the Henry coefficients of H₂O₂ in water in better agreement with experimental values than the force field by Orabi & English.

Lithium (Li) dopants have garnered attention as a means to enhance hydrogen (H₂) binding energies and capacities in 2D boron-based materials. However, it is unclear if and how these dopants affect H₂ dissociation and chemisorption. Using density functional theory (DFT) and nudged elastic band (NEB) calculations, reaction pathways for H₂ dissociation on borophene-hydride and striped-borophene are investigated in the presence of Li dopants. Our results indicate that tuning the Li-loading can increase the reversibility and the rate of dehydrogenation for both borophene-hydride and striped borophene. In particular, for Li-doped borophene-hydride, the heat of reaction for H₂ release is reduced by more than 85% compared to the pristine structure (1.97 eV/H₂). Our results signify that Li-doping can considerably change the H₂ chemisorption properties of striped-borophene and borophene-hydride, and can lead to promising materials for H₂ storage.