Computational study of nitric oxide cation cluster thermodynamics

CHED 966

Kevin M. McLendon,, Sydney H. Ryan,, and Alan C. Goren, Department of Natural Sciences & Mathematics, Transylvania University, 300 North Broadway, Lexington, KY 40508
Nitric oxide has provided chemical physicists studying both cluster and atmospheric chemistry with a wealth of useful information. Nitric oxide is an intriguing molecule for probing the dynamics and structure of van der Waals clusters. In fact, charged (ionic) clusters are attractive model systems both experimentally and theoretically for investigating changes in physical and chemical properties of ions in transition from gas to condensed phases. Cluster studies have attempted to reveal the intrinsic reactivity of molecules imbedded in a “microsolution”. Moreover, cluster work has also succeeded in separating factors governing reactions in solutions which are absent in single molecule gaseous systems. Charged particles play a crucial role in many geophysical phenomena in the atmosphere and radio wave communication would not be possible if not for charged particles. Ionic clusters have often been shown to be the predominant ionic species in the D region of the ionosphere. Not only have chemists used clusters as models for investigating condensed phase systems, but physicists have also used clusters as models for learning about electronic properties in solids. We have calculated the heats of reaction for a series of laser-mediated cluster ion decompositions (A.J. Stace, et al), (NO)x(+1) → (NO)x-2(+1) + 2NO. All calculations were performed using density functional theory with exchange-correlation functional (B3LYP) and 6-31G(d) basis sets. Vibrational frequencies were calculated for all optimized geometries.