Solar emission produces copious nitrosonium ions (NO + ) in the D layer of the ionosphere, 60 to 90 km above the Earth's surface. NO + is believed to transfer its charge to water clusters in that region, leading to the formation of gaseous nitrous acid (HONO) and protonated water cluster. The dynamics of this reaction at the ionospheric temperature (200-220 K) and the associated mechanistic details are largely unknown. Using ab initio molecular dynamics (AIMD) simulations and transition-state search, key structures of the water hydrates-tetrahydrate NO + (H 2 O) 4 and pentahydrate NO + (H 2 O) 5 -are identified and shown to be responsible for HONO formation in the ionosphere. The critical tetrahydrate NO + (H 2 O) 4 exhibits a chainlike structure through which all of the lowest-energy isomers must go. However, most lowest-energy isomers of pentahydrate NO + (H 2 O) 5 can be converted to the HONO-containing product, encountering very low barriers, via a chain-like or a three-armed, star-like structure. Although these structures are not the global minima, at 220 K, most lowest-energy NO + (H 2 O) 4 and NO + (H 2 O) 5 isomers tend to channel through these highly populated isomers toward HONO formation.ionosphere | HONO | mechanism | water | clusters T he ionosphere is the largest layer in the Earth's atmosphere, ranging in altitude from ∼60 to 1,000 km and includes the thermosphere and parts of the mesosphere and exosphere. The ionosphere contains a high concentration of electrons and ions because of the ionization of gases in that region by short wavelength radiation from the Sun. Therefore, these species play an important role in atmospheric electricity, influencing radio propagation to different regions on the Earth's surface and space-based navigational systems (1). The D layer is the innermost layer of the ionosphere, ranging from 60 to 90 km in altitude, where Lyman series-α hydrogen radiation from the Sun gives rise to abundant nitrosonium ions (NO + ). In addition to the ionospheric reaction between NO + and water, explorations of the chemical reactivity of NO + and water clusters (2-4) have implications for understanding the mechanisms of atmospherically relevant reactions in water clusters (5-9).Over the past two decades, several experimental and theoretical studies (10-13) have focused on understanding the chemical and physical properties of the small-sized hydrated nitrosonium ion NO + (H 2 O) n , where n = 1-5. Two key processes have been proposed for HONO formation: NO + ðH 2 OÞ n + H 2 O → fðHONOÞH + ðH 2 OÞ n É → H + ðH 2 OÞ n + HONO .[1]Lee and coworkers (14) used vibrational spectroscopy to obtain clear evidence of the rearrangement of the NO + (H 2 O) n cluster by observing the appearance of new hydrogen (H)-bonded OH stretching lines. Using quantum molecular dynamics, Ye and Cheng (15) suggested possible structures and corresponding IR spectra for NO + (H 2 O) n (n = 1-3) clusters. In a major experimental breakthrough, Relph et al. (16) showed that the extent to which reaction 1 produces HONO ...