dorsal/arxiv
View SchemaSlow periodic oscillations in time domain dynamics of NO2
| Authors | Michael Sanrey, Marc Joyeux |
|---|---|
| Categories | |
| ArXiv ID | physics/0703073 |
| URL | https://arxiv.org/abs/physics/0703073 |
| DOI | 10.1063/1.2446920 |
| Journal | Journal of Chemical Physics 126 (21/02/2007) 074301 |
Abstract
We investigated the time domain nonadiabatic dynamics of NO2 on the coupled X2A1 and A2B2 electronic states by launching wave packets on the excited electronic state and focused on the evolution at long times (t>200 fs), which has received little attention up to now. We showed that the initial fast spreading of the wave packets is followed at all energies by slow periodic intramolecular vibronic energy redistribution (IVER) with periods in the range 0.3 to several tens of ps. These energy transfers lead to oscillations with the same periods in the population of each electronic state. Propagation of wave packets indicates that IVER frequencies also dominate the fluctuations of the squared modulus of the autocorrelation function, |A(t)|^2, at energies not too high above the bottom of the conical intersection, but that this is no longer the case at higher energies. For example, for initial wave packets prepared by almost vertical excitation of the vibrational ground state of the ground electronic surface, the oscillations of |A(t)|^2 essentially reflect the detuning from 1:2 resonance between the frequency of the bend and that of the symmetric stretch in the excited electronic state. These theoretical results were used to discuss the possible origin of the low frequency oscillations which were recently observed in time domain experimental spectra of NO2.
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"abstract": "We investigated the time domain nonadiabatic dynamics of NO2 on the coupled\nX2A1 and A2B2 electronic states by launching wave packets on the excited\nelectronic state and focused on the evolution at long times (t\u003e200 fs), which\nhas received little attention up to now. We showed that the initial fast\nspreading of the wave packets is followed at all energies by slow periodic\nintramolecular vibronic energy redistribution (IVER) with periods in the range\n0.3 to several tens of ps. These energy transfers lead to oscillations with the\nsame periods in the population of each electronic state. Propagation of wave\npackets indicates that IVER frequencies also dominate the fluctuations of the\nsquared modulus of the autocorrelation function, |A(t)|^2, at energies not too\nhigh above the bottom of the conical intersection, but that this is no longer\nthe case at higher energies. For example, for initial wave packets prepared by\nalmost vertical excitation of the vibrational ground state of the ground\nelectronic surface, the oscillations of |A(t)|^2 essentially reflect the\ndetuning from 1:2 resonance between the frequency of the bend and that of the\nsymmetric stretch in the excited electronic state. These theoretical results\nwere used to discuss the possible origin of the low frequency oscillations\nwhich were recently observed in time domain experimental spectra of NO2.",
"arxiv_id": "physics/0703073",
"authors": [
"Michael Sanrey",
"Marc Joyeux"
],
"categories": [
"physics.chem-ph"
],
"doi": "10.1063/1.2446920",
"journal_ref": "Journal of Chemical Physics 126 (21/02/2007) 074301",
"title": "Slow periodic oscillations in time domain dynamics of NO2",
"url": "https://arxiv.org/abs/physics/0703073"
},
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