Issue 22, 2018

Ultrafast excited-state dynamics of 2,5-dimethylpyrrole

Abstract

The ultrafast excited-state dynamics of 2,5-dimethylpyrrole following excitation at wavelengths in the range of 265.7–216.7 nm is studied using the time-resolved photoelectron imaging method. It is found that excitation at longer wavelengths (265.7–250.2 nm) results in the population of the S1(1πσ*) state, which decays out of the photoionization window in about 90 fs. At shorter pump wavelengths (242.1–216.7 nm), the assignments are less clear-cut. We tentatively assign the initially photoexcited state(s) to the 1π3p Rydberg state(s) which has lifetimes of 159 ± 20, 125 ± 15, 102 ± 10 and 88 ± 10 fs for the pump wavelengths of 242.1, 238.1, 232.6 and 216.7 nm, respectively. Internal conversion to the S1(1πσ*) state represents at most a minor decay channel. The methyl substitution effects on the decay dynamics of the excited states of pyrrole are also discussed. Methyl substitution on the pyrrole ring seems to enhance the direct internal conversion from the 1π3p Rydberg state to the ground state, while methyl substitution on the N atom has less influence and the internal conversion to the S1(πσ*) state represents a main channel.

Graphical abstract: Ultrafast excited-state dynamics of 2,5-dimethylpyrrole

Article information

Article type
Paper
Submitted
07 Feb 2018
Accepted
29 Mar 2018
First published
30 Mar 2018

Phys. Chem. Chem. Phys., 2018,20, 15015-15021

Ultrafast excited-state dynamics of 2,5-dimethylpyrrole

D. Yang, Y. Min, Z. Chen, Z. He, K. Yuan, D. Dai, X. Yang and G. Wu, Phys. Chem. Chem. Phys., 2018, 20, 15015 DOI: 10.1039/C8CP00883C

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