The barrier height of the F+H2 reaction revisited: coupled-cluster and multireference configuration-interaction benchmark calculations.
Large scale coupled-cluster benchmark calculations have been carried out to determine the barrier height of the F+H2 reaction as accurately as possible. The best estimates for the barrier height of the linear and bent transition states amount to 2.16 and 1.63 kcal/mol, respectively. These values include corrections for core correlation, scalar-relativistic effects, spin-orbit effects, as well as the diagonal Born-Oppenheimer correction. The CCSD(T) basis-set limits are estimated using extrapolation techniques with augmented quintuple and sextuple-zeta basis sets, and remaining N-electron errors are determined using coupled-cluster singles, doubles, triples, quadruples calculations with up to augmented quintuple-zeta basis sets. The remaining uncertainty is estimated to be less than 0.1 kcal/mol. The coupled-cluster results are used to calibrate multireference configuration-interaction calculations with empirical scaling of the correlation energy.
Werner
Hans-Joachim
HJ
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany. werner@theochem.uni-stuttgart.de
Kállay
Mihály
M
Gauss
Jürgen
J