H_2O-Mediated Trimerization of H_2SO_4: A Computational Study and Comparison with Experimental Data

摘要

In the present paper, the formation of stable hydrated (H_2SO_4)_3(H_2O)_n clusters has been studied using the Density Functional Theory (DFT) at PW91PW91/6-311++(3df,3pd) level. We have found that the hydration of H_2SO_4 trimers is stronger than that of H_2SO_4 dimers and tends to decrease at large hydration numbers. We have shown that the affinity of H_2SO_4 to (H_2SO_4)_2(H_2O)_n is much higher than that H_2SO_4 to (H_2SO_4) (H_2O)_n. We have compared the equilibrium constants of H_2O-mediated trimerization of H_2SO_4 obtained using PW91PW91/6-311++(3df,3pd) method with experimental data and found that theory and experimentation are in good agreement. The new thermochemical data can be used in a wide range of nucleation studies and can be utilized for the development of quantum-based models of nucleation rates.