Role of conical intersection seam topography in the chemiexcitation of 1,2-dioxetanes

24 December 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Chemiexcitation, the generation of electronic excited states by a thermal reaction initiated on the ground state, is an essential step in chemiluminescence, and it is mediated by the presence of a conical intersection that allows a nonadiabatic transition from ground state to excited state. Conical intersections classified as sloped favor chemiexcitation over ground state relaxation. The chemiexcitation yield of 1,2-dioxetanes is known to increase upon methylation. In this work we explore to which extent this trend can be attributed to changes in the conical intersection topography or accessibility. Since conical intersections are not isolated points, but continuous seams, we locate regions of the conical intersection seams that are close to the configuration space traversed by the molecules as they react on the ground state. We find that conical intersections are energetically and geometrically accessible from the reaction trajectory, and that topographies favorable to chemiexcitation are found in all three molecules studied. Nevertheless, the results suggest that dynamic effects are more important for explaining the different yields than the static features of the potential energy surfaces.

Keywords

chemiexcitation
chemiluminescence
conical intersection
pontential energy surface

Supplementary materials

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Supplementary information
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Transition dipole moments along the reference trajectories.
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Structure files
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Geometries of the three studied molecules, 0Me, 1Me and 2Me, for the reference trajectories, and for the optimized conical intersection "valleys".
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