Ab initio methods for reactive potential surfaces.
Case studies of ten reactions using a variety of standard electronic structure methods are presented. These case studies are used to illustrate the usefulness and shortcomings of these standard methods for various classes of reactions. Limited comparisons with experiment are made. The reactions studied include four radical-radical combinations, H + CH(3)--> CH(4), CH(3) + CH(3)--> C(2)H(6), H + HCO --> H(2)CO and CH(3) + HCO --> CH(3)CHO, three abstraction reactions, H + HO(2)--> H(2) + O(2), H + HCO --> H(2) + CO and CH(3) + HCO --> CH(4) + CO, a radical-molecule addition, H + HCCH --> C(2)H(3), and two molecular decompositions, H(2)CO --> H(2) + CO and CH(3)CHO --> CH(4) + CO. The electronic structure methods used are DFT, MP2, CCSD(T), QCISD(T), CASSCF, CASPT2, and CAS+1+2+QC.
Harding
Lawrence B
LB
Chemistry Division, Argonne National Laboratory, Argonne, IL 60439, USA. harding@anl.gov
Klippenstein
Stephen J
SJ
Jasper
Ahren W
AW
D000465:Algorithms; D002621:Chemistry / Q000379:methods; D002627:Chemistry, Physical / Q000379:methods*; D004581:Electronics; D007700:Kinetics; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D016011:Normal Distribution; D011312:Pressure; D011789:Quantum Theory; D013499:Surface Properties; D013696:Temperature