| Autor: |
Hunter KE; Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States., Mao Y; Department of Chemistry and Biochemistry, San Diego State University, San Diego, California 92182, United States., Chin AW; Sorbonne Université, CNRS, Institut des NanoSciences de Paris, 4 place Jussieu, Paris 75005, France., Zuehlsdorff TJ; Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States. |
| Abstrakt: |
Nonadiabatic couplings between several electronic excited states are ubiquitous in many organic chromophores and can significantly influence optical properties. A recent experimental study demonstrated that the proflavine molecule exhibits surprising dual fluorescence in the gas phase, which is suppressed in polar solvent environments. Here, we uncover the origin of this phenomenon by parametrizing a linear-vibronic coupling Hamiltonian from spectral densities of system-bath coupling constructed along molecular dynamics trajectories, fully accounting for interactions with the condensed-phase environment. The finite-temperature absorption, steady-state emission, and time-resolved emission spectra are then computed using powerful, numerically exact tensor network approaches. We find that the dual fluorescence in vacuum is driven by a single well-defined coupling mode but is quenched in solution due to dynamic solvent-driven symmetry breaking that mixes the two low-lying electronic states. We expect the computational framework developed here to be widely applicable to the study of non-Condon effects in complex condensed-phase environments. |
