Excited state non-adiabatic dynamics of pyrrole: a time-resolved photoelectron spectroscopy and quantum dynamics study

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Excited state non-adiabatic dynamics of pyrrole : a time-resolved photoelectron spectroscopy and quantum dynamics study. / Wu, Guorong; Neville, Simon P; Schalk, Oliver; Sekikawa, Taro; Ashfold, Michael N R; Worth, Graham A; Stolow, Albert.

In: Journal of Chemical Physics, Vol. 142, No. 7, 074302, 21.02.2015.

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@article{75489f430c614a5eb903aa67ba22e433,
title = "Excited state non-adiabatic dynamics of pyrrole: a time-resolved photoelectron spectroscopy and quantum dynamics study",
abstract = "The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole's electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A2(πσ∗) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A1(ππ∗) and B2(ππ∗) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole's electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B1(πσ∗) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B1(πσ∗) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A2(πσ∗) state.",
keywords = "Journal Article",
author = "Guorong Wu and Neville, {Simon P} and Oliver Schalk and Taro Sekikawa and Ashfold, {Michael N R} and Worth, {Graham A} and Albert Stolow",
year = "2015",
month = feb,
day = "21",
doi = "10.1063/1.4907529",
language = "English",
volume = "142",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics",
number = "7",

}

RIS

TY - JOUR

T1 - Excited state non-adiabatic dynamics of pyrrole

T2 - a time-resolved photoelectron spectroscopy and quantum dynamics study

AU - Wu, Guorong

AU - Neville, Simon P

AU - Schalk, Oliver

AU - Sekikawa, Taro

AU - Ashfold, Michael N R

AU - Worth, Graham A

AU - Stolow, Albert

PY - 2015/2/21

Y1 - 2015/2/21

N2 - The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole's electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A2(πσ∗) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A1(ππ∗) and B2(ππ∗) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole's electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B1(πσ∗) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B1(πσ∗) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A2(πσ∗) state.

AB - The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole's electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A2(πσ∗) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A1(ππ∗) and B2(ππ∗) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole's electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B1(πσ∗) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B1(πσ∗) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A2(πσ∗) state.

KW - Journal Article

U2 - 10.1063/1.4907529

DO - 10.1063/1.4907529

M3 - Article

C2 - 25702010

VL - 142

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 7

M1 - 074302

ER -