Collision-partner dependence of energy transfer between the CH A2Delta and B2Sigma- states.
We have investigated experimentally the collision-induced electronic energy transfer between the CH A(2)Delta and B(2)Sigma(-) states with the series of partners He, Ar, H(2), N(2), CO, and CO(2). Single rovibronic states of either of the near-degenerate levels A(2)Delta, v = 1, or B(2)Sigma(-), v = 0, were prepared by laser excitation. Collisional transfer processes were monitored by detecting dispersed, time-resolved fluorescence from the initial and product states. The microscopic rate constants for vibronically resolved transfer between the A(2)Delta and B(2)Sigma(-) states, vibrational relaxation within the A state, and total removal to unobserved final products were determined for each partner. In line with previous work, we find that only CO and H(2) are efficient at total removal of CH A(2)Delta and B(2)Sigma(-), most probably through chemical reaction. CO(2) is notably effective at A(2)Delta state vibrational relaxation, possibly through resonant vibrational energy transfer. All the partners cause transfer between CH A(2)Delta and B(2)Sigma(-). An important new observation is that their efficiencies are well correlated with the strength of long-range attractive forces, as revealed through a positive correlation of the Parmenter-Seaver type. The vibronic branching to A(2)Delta, v = 0 and 1 from B(2)Sigma(-), v = 0 is found to be significantly collision-partner-dependent and not well predicted by energy gap scaling laws. We do not find any enhanced effectiveness in B(2)Sigma(-) to A(2)Delta coupling for those partners which form strongly bound intermediates, suggesting that this specific electronic channel is controlled by different regions of the potential energy surfaces.
Richmond
Graham
G
School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UK.
Costen
Matthew L
ML
McKendrick
Kenneth G
KG