| DOI | Resolve DOI: https://doi.org/10.1063/1.4938423 |
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| Author | Search for: Wu, Guorong1; Search for: Neville, Simon P.; Search for: Schalk, Oliver2; Search for: Sekikawa, Taro; Search for: Ashfold, Michael N. R.; Search for: Worth, Graham A.; Search for: Stolow, Albert3 |
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| Name affiliation | - National Research Council of Canada
- National Research Council of Canada. NRC Steacie Institute for Molecular Sciences
- National Research Council of Canada. Security and Disruptive Technologies
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| Format | Text, Article |
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| Subject | calculations; dynamics; photoelectron spectroscopy; photoelectrons; photoionization; photons; quantum theory; Rydberg states; wave packets; excitation wavelength; non-adiabatic dynamics; photoionization cross section; quantum dynamics calculations; three orders of magnitude; time-dependent Hartree method; time-resolved photoelectron spectroscopy; vibrational excitation; excited states |
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| Abstract | The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A2(πσ-) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B1(π3py) Rydberg state, followed by prompt internal conversion to the A2(πσ-) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A2(πσ-) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A2(πσ-) state, facilitating wavepacket motion around the potential barrier in the N-CH3 dissociation coordinate. |
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| Publication date | 2016-01-07 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 21277473 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction |
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| Record identifier | aeb76744-a526-4c68-a827-aaee557fb916 |
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| Record created | 2016-03-09 |
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| Record modified | 2020-03-16 |
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