dorsal/arxiv
View SchemaQuantum mechanical and quasiclassical investigation of the time domain nonadiabatic dynamics of NO2 close to the bottom of the X2A1-A2B2 conical intersection
| Authors | Michaël Sanrey, Marc Joyeux |
|---|---|
| Categories | |
| ArXiv ID | physics/0605137 |
| URL | https://arxiv.org/abs/physics/0605137 |
| DOI | 10.1063/1.2211609 |
| Journal | Journal of Chemical Physics, 125 (2006) 014304 |
Abstract
We use the effective Hamiltonian that we recently fitted against the first 306 experimentally observed vibronic transitions of NO2 [J. Chem. Phys. 119, 5923 (2003)] to investigate the time domain nonadiabatic dynamics of this molecule on the coupled X2A1 and A2B2 electronic states, using both quantum mechanical and quasiclassical techniques. From the quantum mechanical point of view, we show that the transfer of population to the electronic ground state originating from a wave packet launched on the excited state occurs in a stepwise fashion. The evolution of wave packets launched on the electronic ground state is instead more complex because the crossing seam is located close to the bottom of the electronic excited state. We next use the mapping formalism, which replaces the discrete electronic degrees of freedom by continuous ones, to obtain a classical description of the coupled electronic states. We propagate gaussian swarms of trajectories to show that this approach can be used to calculate the populations in each electronic state. We finally propose a very simple trajectory surface hopping model, which assumes that trajectories have a constant probability to jump onto the other state in a particular region of the phase space and a null hopping probability outside from this region. Quasiclassical calculations show that this model enables a precise estimation of complex quantities, like for example the projection of the instantaneous probability density on given planes.
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"abstract": "We use the effective Hamiltonian that we recently fitted against the first\n306 experimentally observed vibronic transitions of NO2 [J. Chem. Phys. 119,\n5923 (2003)] to investigate the time domain nonadiabatic dynamics of this\nmolecule on the coupled X2A1 and A2B2 electronic states, using both quantum\nmechanical and quasiclassical techniques. From the quantum mechanical point of\nview, we show that the transfer of population to the electronic ground state\noriginating from a wave packet launched on the excited state occurs in a\nstepwise fashion. The evolution of wave packets launched on the electronic\nground state is instead more complex because the crossing seam is located close\nto the bottom of the electronic excited state. We next use the mapping\nformalism, which replaces the discrete electronic degrees of freedom by\ncontinuous ones, to obtain a classical description of the coupled electronic\nstates. We propagate gaussian swarms of trajectories to show that this approach\ncan be used to calculate the populations in each electronic state. We finally\npropose a very simple trajectory surface hopping model, which assumes that\ntrajectories have a constant probability to jump onto the other state in a\nparticular region of the phase space and a null hopping probability outside\nfrom this region. Quasiclassical calculations show that this model enables a\nprecise estimation of complex quantities, like for example the projection of\nthe instantaneous probability density on given planes.",
"arxiv_id": "physics/0605137",
"authors": [
"Micha\u00ebl Sanrey",
"Marc Joyeux"
],
"categories": [
"physics.chem-ph"
],
"doi": "10.1063/1.2211609",
"journal_ref": "Journal of Chemical Physics, 125 (2006) 014304",
"title": "Quantum mechanical and quasiclassical investigation of the time domain nonadiabatic dynamics of NO2 close to the bottom of the X2A1-A2B2 conical intersection",
"url": "https://arxiv.org/abs/physics/0605137"
},
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