Sulfuric Acid and Sulfuric Acid Hydrates in the Gas Phase: A DFT Investigation

Abstract

The gaseous sulfuric acid and its hydrates play an essential role in the formation and evolution of atmospheric aerosols via nucleation of binary sulfuric acid−water vapors. Recently, it has been pointed out that the dipole moment of vapor molecules and small preexisting clusters is a new parameter controlling the nucleation rates. In this paper, the dipole moments of the mono-, di-, and trihydrates of the sulfuric acid are calculated for the first time. We also report on the molecular structures, energies, vibrational frequencies, absorption intensities and dipole moments of the hydrates and compare our model predictions with the results of other studies. The density functional theory (DFT) calculations have been carried out using the PW91 method and TZP basis set. We have determined the optimized conformations of gas-phase sulfuric acid and mono-, di-, and trihydrates of sulfuric acid using different starting scenarios and computed their dipole moments. The obtained results can be utilized directly in the modeling of the atmospheric aerosol formation and they are applied for the analysis of the hydration thermodynamics.