Importance of the lowest-lying Π electronic state in the photodissociation dynamics of LiF
In addition to the well-known 1(1)Sigma(+) and 2(1)Sigma(+) electronic states which are nonadiabatically coupled and responsible for the ionic-covalent transition in lithium fluoride (LiF), the lowest-lying Pi state is included in the present dynamical treatment. Although this purely repulsive 1(1)P...
Elmentve itt :
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| Dokumentumtípus: | Cikk |
| Megjelent: |
2018
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| Sorozat: | CHEMICAL PHYSICS
515 |
| Tárgyszavak: | |
| doi: | 10.1016/j.chemphys.2018.05.002 |
| mtmt: | 30548515 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/27752 |
| Tartalmi kivonat: | In addition to the well-known 1(1)Sigma(+) and 2(1)Sigma(+) electronic states which are nonadiabatically coupled and responsible for the ionic-covalent transition in lithium fluoride (LiF), the lowest-lying Pi state is included in the present dynamical treatment. Although this purely repulsive 1(1)Pi state lies energetically close to the 2(1)Sigma(+) one and has a remarkable transition dipole moment with the 1(1)Sigma(+) ground electronic state in the Franck-Condon region, it is often excluded in studies on the photodissociation of LiF.Here we demonstrate the important role of 1(1)Pi by comparing two-state (1(1)Sigma(+) and 2(1)Sigma(+)) and three-state (1(1)Sigma(+), 2(1)Sigma(+) and 1(1)Pi) nuclear dynamical simulations focusing on the electronic state populations. Both for short (tau = 20 fs) and long (tau = 100 fs) laser pulses in the energy interval of h omega = 6.2 eV-7.35 eV we find that the population of 1(1)Pi can significantly exceed that of 2(1)Sigma(+). Furthermore we consider rotating molecules and reveal a faster dissociation compared to the case where only the vibration of the molecules are treated. (C) 2018 Elsevier B.V. All rights reserved. |
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| Terjedelem/Fizikai jellemzők: | 418-426 |
| ISSN: | 0301-0104 |