Anomalously Large Difference in Dipole Moment of Isomers with Nearly Identical Thermodynamic Stability

Abstract

Sulfuric acid is a primary atmospheric nucleation precursor, with the ability to form stable aqueous hydrogen-bonded clusters/complexes. The electrical dipole moment of such clusters/complexes is important for ion-induced nucleation, largely controlled by dipole-charge interaction of airborne ions with vapor monomers and pre-existing clusters. Although experiments typically trace a single lowest energy conformer at low temperatures, the present study shows that the immediate vicinity (<1 kcal mol (-1)) of the global minima may be populated with a number of isomers of nearly identical spectral characteristics and drastically different dipole moments. The difference in the dipole moment of mono-, di-, and trihydrates of the sulfuric acid exceeds 1.3-1.5 Debyes ( approximately 50-60%), 1.4-2.6 Debyes ( approximately 50-90%), and 3.8-4.2 Debyes ( approximately 370-550%), respectively. Being driven by the temperature dependence of the Boltzmann distribution, the difference between the Boltzmann-Gibbs average dipole moment and the dipole moment of the most stable isomer increases with the ambient temperature, leading to large variations in the dipole-ion interaction strength, which may have important implications for the ion-mediated production of ultrafine aerosol particles associated with various climatic and health impacts.