Evolution of the linker in microhydrated hydrogen dinitrate anions: From H+ to H5O2

Hydrogen dinitrate anion, HNO3(NO3−), is a proton‐bound dimer with a very strong hydrogen bond. By employing ab initio molecular dynamics (AIMD) method, we studied the effects of the proton transfer and the rotation of the nitrates on the vibrational profiles of HNO3(NO3−)(H2O)n (n = 0–2). The AIMD results indicate that the structure of the n = 0 cluster is very flexible, even though its hydrogen bond is quite strong. Significant rotations around the hydrogen bond and frequent transfers of proton from HNO3 to NO3− are observed in AIMD simulations. Dynamic changes are therefore an important factor in understanding the broadening of vibrational features. For n = 1, the extent of structural fluctuation increases further, as H2O could move around the anion while the HNO3(NO3−) core also goes through structural changes. Its vibrational spectrum can be understood as a mixture of many isomers visited during AIMD simulations. By n = 2, the structure is stabilized around one isomer, with the linker between the two nitrates being H5O2+, rather than H+. Due to strong hydrogen bonds between nitrates and water molecules, this H5O2+ takes the extraordinary structure with the H+ localized on one H2O, rather than being shared. While this novel structure is stable during AIMD simulations, the dynamic fluctuations in hydrogen bond distances still produce significant broadening in its vibrational profile. The effects of the proton transfer and the rotation of the nitrates on the vibrational profiles of HNO3(NO3−)(H2O)n at finite temperature have been studied using ab initio molecular dynamics simulations. The results reveal the evolution of the linker between the two nitrates from H+ at n = 0 and 1 to H5O2+ at n = 2.