Recent advances in the chemistry of electronically excited atoms

Rotational surprisals and energy disposal from statistical simulations of the crossed beam reaction C (3P) + NO → CN (υ) + O(3P)

Measurements are reported wherein Hg(6 3P0) is de‐excited by collisions with HgBr(X 2Σ), Br(4 2P), and Br2(X 1Σ). In the cases of HgBr(X 2Σ) and Br(4 2P), quenching rate coefficients are larger than hard‐sphere collision rate coefficients, and are consistent with ion‐pair formation via the harpoon mechanism. Because of the radical–radical nature of the interaction, long‐range attractive forces can draw the nuclei toward the region of coupling with the ion‐pair surface, thereby catalyzing ion‐pair formation. The ion‐pair thus produced correlates with HgBr(B 2Σ), and provides a direct pathway for channeling metastable Hg(6 3P0) excitation into HgBr(B 2Σ), the upper state of the HgBr(B→X) laser. Quenching of Hg(6 3P0) by Br2(X 1Σ) is an order of magnitude less efficient than the above processes, and reasons for this are discussed.

The collisional de‐excitation of Hg(6 3P0) by HgBr(X 2Σ), Br(4 2P), and Br2(X 1Σ): Evidence for ion‐pair formation in the entrance channel

Rate constants for the collisional deactivation of Bi 6p3(2D°3/2) and 6p3(2D°5/2) are reported for these states by Ar, Xe, N2, H2, D2, CO, O2, CO2, and SF6 at room temperature. The excited atoms were produced by the flash photodecomposition of trimethyl bismuth and concentrations of these excited states were monitored by time resolved atomic resonance absorption techniques. Comparison of these results is made with the quenching rate constants for these states reported by M. J. Bevan and D. Husain, J. Phys. Chem. 80, 217 (1976).

Recent advances in the chemistry of electronically excited atoms

Citations

Rotational surprisals and energy disposal from statistical simulations of the crossed beam reaction C (3P) + NO → CN (υ) + O(3P)

The collisional de‐excitation of Hg(6 3P0) by HgBr(X 2Σ), Br(4 2P), and Br2(X 1Σ): Evidence for ion‐pair formation in the entrance channel

Collisional relaxation of electronically excited bismuth: 6p3(2D°3/2) and 6p3(2D°5/2)

Chapter 8 – the role of metastable particles in collision processes

4 – Production and Detection of Reactive Species with Lasers in Static Systems

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