Computational study of isoprene hydroxyalkyl peroxy radical-water complexes (C5H8(OH)O2-H2O).
Herein we report an extensive ab initio study on the existence of eight beta-hydroxy isoprene peroxy radical-water complexes. Binding energies calculated at the MP2(full)/6-311++G(2d,2p)//CCSD(T)/6-311++G(d,p) level of theory range between 3.85 and 5.66 kcal mol(-1). The results of natural bond orbital calculations are presented to help rationalize complex formation. Atmospheric lifetimes, equilibrium constants, heats of formation, and the relative abundance of complexed to uncomplexed peroxy radicals are also reported and discussed.
Clark
Jared
J
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, USA.
Call
Seth T
ST
Austin
Daniel E
DE
Hansen
Jaron C
JC
D001272:Atmosphere; D002070:Butadienes / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D045782:Hemiterpenes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010420:Pentanes / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D002070:Butadienes; D005609:Free Radicals; D045782:Hemiterpenes; D010420:Pentanes; D010545:Peroxides; D014867:Water; C005059:isoprene