Dynamics of the S(D21)+HD(j=0) reaction at collision energies approaching the cold regime: A stringent test for theory

Abstract

We report integral cross sections for the S(1D 2)+HD(j=0) →DS+H and HS+D reaction channels obtained through crossed-beam experiments reaching collision energies as low as 0.46 meV and from adiabatic time-independent quantum-mechanical calculations. While good overall agreement with experiment at energies above 10 meV is observed, neither the product channel branching ratio nor the low-energy resonancelike features in the HS+D channel can be theoretically reproduced. A nonadiabatic treatment employing highly accurate singlet and triplet potential energy surfaces is clearly needed to resolve the complex nature of the reaction dynamics. © 2012 American Physical Society.