Neville, SP; Mirmiran, A; Worth, GA; Schuurman, MS; (2019) Electron transfer in photoexcited pyrrole dimers. Journal of Chemical Physics , 151 (16) , Article 164304. 10.1063/1.5120006.

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Abstract

Following on from previous experimental and theoretical work [Neville et al., Nat. Commun. 7, 11357 (2016)], we report the results of a combined electronic structure theory and quantum dynamics study of the excited state dynamics of the pyrrole dimer following excitation to its first two excited states. Employing an exciton-based analysis of the Ã(π3s/σ*) and ˜ B (π3s/3p/σ*) states, we identify an excited-state electron transfer pathway involving the coupling of the Ã(π3s/σ*) and ˜ B (π3s/3p/σ*) states and driven by N–H dissociation in the ˜ B (π3s/3p/σ*) state. This electron transfer mechanism is found to be mediated by vibronic coupling of the ˜ B state, which has a mixed π3s/3p Rydberg character at the Franck-Condon point, to a high-lying charge transfer state of the πσ* character by the N–H stretch coordinate. Motivated by these results, quantum dynamics simulations of the excited-state dynamics of the pyrrole dimer are performed using the multiconfigurational time-dependent Hartree method and a newly developed model Hamiltonian. It is predicted that the newly identified electron transfer pathway will be open following excitation to both the Ã(π3s/σ*) and ˜ B (π3s/3p/σ*) states and may be the dominant relaxation pathway in the latter case.

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