Effects of hexamethylenetetramine (HMTA) on the aqueous solution structure, dynamics and ion solvation scenario: A concentration and temperature dependent study with potential HMTA models

The local hydrogen bonding structure of water and its dynamics in hexamethylenetetramine (HMTA) solution is investigated by using classical molecular dynamics simulations. In this study, we have compared two potential HMTA models with different Lennard-Jones (L-J) combination rules. We have considered five different concentrations of HMTA, ranging from pure water to 6.181 m HMTA at 298 K, whereas to calculate the temperature dependence from 298 K to 353 K, we have used 4.187 m concentration of HMTA. From the radial distribution function, it is observed that the addition of HMTA facilitates structural making of water, whereas our calculated values of the tetrahedral order parameter and asphericity of water suggests disordered structure with increasing HMTA concentration. Also there is a significant development of self-aggregation among water and HMTA molecules at higher concentration of HMTA. The self-diffusion coefficient values of water and HMTA is found to be decreased with increasing HMTA concentration in the solution, whereas at concentrations below 1.0 m, it matches well with the experimental observations. Our calculated activation energy of diffusion for HMTA (4.10 ± 0.2 kcal/g mol for Model-II), is very close to the experimental observation (4.34–4.44 kcal/g mol). The structure of the hydration shell of ions of different charges and sizes is also investigated in the presence of HMTA. For all the models, it is observed that the structural and dynamical properties of water and the hydration shell of ion shows negligible difference with varying concentration and temperature. In contrast, the ion−HMTA correlations are model dependent. It is suggested that the HMTA model-I (AM) is the suitable model for representing ion-solvation structure and dynamics particularly at lower concentrations of aqueous-HMTA solution. [Display omitted] •HMTA models with different L-J combination rules are examined.•DHMTA at lower concentration agrees well with experimental results.•Whereas DWater matches reasonably well even at higher concentration.•Solvation structure and dynamics of ions/atom (Na+,K+,Cl−/Cl0) were investigated.•HMTA model-I (AM) is suggested for ion solvation studies at lower concentrations.