Complexes of HNO3 and NO3- with NO2 and N2O4, and their potential role in atmospheric HONO formation

Abstract

Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO3)·(NO2), (HNO3)·(N2O4), (NO3-)·(NO2), and (NO3-)·(N2O4). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO3-)·(N2O4) possessing binding energy of almost -14 kcal mol-1. Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm-1 that are attributed to NO2 complexed to NO3- and HNO3, respectively. The electronic states of (HNO3)·(N2O4) and (NO3-)·(N2O4) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO3-)·(N2O4) was obtained from UV/vis absorption spectra of N2O4 in concentrated HNO3, which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N2O4 dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO3)·(NO2) and (HNO3)·(N2O4) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies. © 2008 the Owner Societies.