Benchmark calculations of the complete configuration-interaction limit of Born-Oppenheimer diagonal corrections to the saddle points of isotopomers of the H + H2 reaction.
We present a detailed ab initio study of the effect that the Born-Oppenheimer diagonal correction (BODC) has on the saddle-point properties of the H3 system and its isotopomers. Benchmark values are presented that are estimated to be within 0.1 cm(-1) of the complete configuration-interaction limit. We consider the basis set and correlation treatment requirements for accurate BODC calculations, and both are observed to be more favorable than for the Born-Oppenheimer energies. The BODC raises the H + H2 barrier height by 0.1532 kcal/mol and slightly narrows the barrier--with the imaginary frequency increasing by approximately 2%.
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA. slmielke@chem.northwestern.edu
Steven L
SL
Mielke
David W
DW
Schwenke
Kirk A
KA
Peterson