TY - JOUR
T1 - Model studies of intersystem crossing effects in the O + H2 reaction
AU - Hoffmann, Mark R.
AU - Schatz, George C.
PY - 2002/1/1
Y1 - 2002/1/1
N2 - We use quantum scattering and trajectory surface hopping methods to examine the influence of intersystem crossing between the lowest energy triplet and singlet states on the O(3P) + H2 reaction dynamics. Several two-state reaction path models of the potential energy surfaces and spin-orbit coupling are studied. In these models, the triplet state curve shows a barrier along the reaction path and the singlet state a well such that the two states intersect at a location near the barrier top. Eleven choices of the parameters in the Hamiltonian are examined in which the effect of the triplet-singlet crossing location, the singlet well depth, and the size and coordinate dependence of the spin-orbit coupling are varied. The quantum calculations show that if the crossing occurs on the reagent side of the triplet barrier, and the spin-orbit coupling at that point is similar to what exists in the reagent O atom, then the low energy reactivity is dominated by intersystem crossing.
AB - We use quantum scattering and trajectory surface hopping methods to examine the influence of intersystem crossing between the lowest energy triplet and singlet states on the O(3P) + H2 reaction dynamics. Several two-state reaction path models of the potential energy surfaces and spin-orbit coupling are studied. In these models, the triplet state curve shows a barrier along the reaction path and the singlet state a well such that the two states intersect at a location near the barrier top. Eleven choices of the parameters in the Hamiltonian are examined in which the effect of the triplet-singlet crossing location, the singlet well depth, and the size and coordinate dependence of the spin-orbit coupling are varied. The quantum calculations show that if the crossing occurs on the reagent side of the triplet barrier, and the spin-orbit coupling at that point is similar to what exists in the reagent O atom, then the low energy reactivity is dominated by intersystem crossing.
UR - http://www.scopus.com/inward/record.url?scp=0042366322&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0042366322&partnerID=8YFLogxK
U2 - 10.1021/bk-2002-0828.ch016
DO - 10.1021/bk-2002-0828.ch016
M3 - Article
AN - SCOPUS:0042366322
VL - 828
SP - 329
EP - 345
JO - ACS Symposium Series
JF - ACS Symposium Series
SN - 0097-6156
ER -