PROBING CHEMICAL-REACTIONS - EVIDENCE FOR EXPLORATION OF AN EXCITED POTENTIAL-ENERGY SURFACE AT THERMAL ENERGIES

The reaction K + NaBr --> KBr + Na is probed during the reactive collision by a continuous wave laser tuned to frequencies not resonant with excitation in either reagents or products. Transient [K..Br..Na] absorbs a laser photon giving [K..Br..Na], which can decompose to Na + KBr. Emission from excited Na at the sodium D lines provides direct evidence of laser absorption during the reaction. Different excitation spectra were observed, depending on which sodium D line was monitored. This difference is explicable if, in the absence of the laser, the reaction flux partially bifurcates to a second potential energy surface during the reaction.