Structure and Abundance of Nitrous Oxide Complexes in Earth’s Atmosphere

Abstract

We have investigated the lowest energy structures and binding energies of a series of atmospherically relevant nitrous oxide (N2O) complexes using explicitly correlated coupled cluster theory. Specifically, we have considered complexes with nitrogen (N2-N2O), oxygen (O2-N2O), argon (Ar-N2O), and water (H2O-N2O). We have calculated rotational constants and harmonic vibrational frequencies for the complexes and the constituent monomers. Statistical mechanics was used to determine the thermodynamic parameters for complex formation as a function of temperature and pressure. These results, in combination with relevant atmospheric data, were used to estimate the abundance of N2O complexes in Earth's atmosphere as a function of altitude. We find that the abundance of N2O complexes in Earth's atmosphere is small but non-negligible, and we suggest that N2O complexes may contribute to absorption of terrestrial radiation and be relevant for understanding the atmospheric fate of N2O.

Complex between Formic Acid and Nitrous Oxide: A Matrix-Isolation and Computational Study

“…Formic acid (HCOOH, FA) and nitrous oxide (N 2 O) participate in atmospheric chemistry. Formic acid is one of the major contributors to rainwater acidity in polluted and remote regions. , Nitrous oxide has a global warming potential nearly 300 times that of carbon dioxide and is one of the largest contributors to ozone depletion in the stratosphere. , Recent studies indicate that the FA and N 2 O annual emissions from known sources may have been significantly underestimated and suggest that these species might be more important to atmospheric chemistry than previously believed. , In addition, FA and N 2 O have been detected in interstellar molecular clouds and are relevant to studies of prebiotic species in astrochemistry. − The interest in noncovalent interactions of FA and N 2 O is considerable. − The formation of weakly bound complexes can cause changes in the stability and reactivity of the constituent monomers. − Quantum mechanical tunneling observed in FA is an exciting phenomenon that can affect the dynamics of the reactions and open new chemical reaction channels. , …”

Selective Electrocatalytic Reduction of Nitrous Oxide to Dinitrogen with an Iron Porphyrin Complex

“…Prior studies indicate that N 2 O, − like CO 2 , can form a hydrated complex with H 2 O. The equilibrium constant is small, although the only measurements that have been made are in the gas phase.…”

Theoretical insights into the structure, stability, thermochemistry, and bonding in hydrated N2O clusters

“…The most stable geometries have only positive frequencies which indicates they are all in the minima in the potential energy surface and are not the saddle points. The thermodynamic parameters and the equilibrium constant for the formation of N 2 O Wn (n = 1-12) are computed using the harmonic oscillator and rigid rotor approximations as speci ed in the previous work [27].…”

“…complexes by matching the computed chemical shift and the experimental chemical shift [26]. Recently, using thermodynamic parameters derived from statistical mechanics, the complex formation as a function of temperature and pressure was reported by Lane and coworkers [27]. Very recently Demaison and coworkers, using the coupled-cluster with single, double, and perturbative triples [CCSD(T)] level coupled with extrapolation of rotational constants calculated with different basis sets determined the accurate equilibrium structure of N 2 O molecules [28].…”