TY - JOUR

T1 - Ab initio studies of O-2(-) (H2O)(n) and O-3(-) (H2O)(n) anionic molecular clusters, n

A1 - Bork,Nicolai Christian

A1 - Kurten,T.

A1 - Enghoff,Martin Andreas Bødker

A1 - Pedersen,Jens Olaf Pepke

A1 - Mikkelsen,K. V.

A1 - Svensmark,Henrik

AU - Bork,Nicolai Christian

AU - Kurten,T.

AU - Enghoff,Martin Andreas Bødker

AU - Pedersen,Jens Olaf Pepke

AU - Mikkelsen,K. V.

AU - Svensmark,Henrik

PB - Copernicus GmbH

PY - 2011

Y1 - 2011

N2 - An ab initio study of gaseous clusters of O-2(-) and O-3(-) with water is presented. Based on thorough scans of configurational space, we determine the thermodynamics of cluster growth. The results are in good agreement with benchmark computational methods and existing experimental data. We find that anionic O-2(-)(H2O)n and O-3(-)(H2O)n clusters are thermally stabilized at typical atmospheric conditions for at least n = 5. The first 4 water molecules are strongly bound to the anion due to delocalization of the excess charge while stabilization of more than 4 H2O is due to normal hydrogen bonding. Although clustering up to 12 H2O, we find that the O-2 and O-3 anions retain at least ca. 80 % of the charge and are located at the surface of the cluster. The O-2(-) and O-3(-) speicies are thus accessible for further reactions. We consider the distributions of cluster sizes as function of altitude before finally, the thermodynamics of a few relevant cluster reactions are considered.

AB - An ab initio study of gaseous clusters of O-2(-) and O-3(-) with water is presented. Based on thorough scans of configurational space, we determine the thermodynamics of cluster growth. The results are in good agreement with benchmark computational methods and existing experimental data. We find that anionic O-2(-)(H2O)n and O-3(-)(H2O)n clusters are thermally stabilized at typical atmospheric conditions for at least n = 5. The first 4 water molecules are strongly bound to the anion due to delocalization of the excess charge while stabilization of more than 4 H2O is due to normal hydrogen bonding. Although clustering up to 12 H2O, we find that the O-2 and O-3 anions retain at least ca. 80 % of the charge and are located at the surface of the cluster. The O-2(-) and O-3(-) speicies are thus accessible for further reactions. We consider the distributions of cluster sizes as function of altitude before finally, the thermodynamics of a few relevant cluster reactions are considered.

U2 - 10.5194/acp-11-7133-2011

DO - 10.5194/acp-11-7133-2011

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

SN - 1680-7316

IS - 14

VL - 11

SP - 7133

EP - 7142

ER -