Abstract
We have theoretically studied the nonadiabatic transitions among the five lower states with the Ω=1u symmetry (1u(1) to 1u(5)) in the photodissociation of Cl2, Br2, and I2 by using the spin-orbit configuration interaction (SOCI) method and the semiclassical time-dependent coupled Schrödinger equations. From the configuration analyses of the SOCI wavefunctions, we found that the nonadiabatic transition between 1u(2) and 1u(1) is a noncrossing type, while that between 1u(3) and 1u(4) is a crossing type for all the molecules. The behavior of the radial derivative coupling element between 1u(1) and 1u(2) and that between 1u(3) and 1u(4) is analyzed in detail. In Cl2, nonadiabatic transitions can take place even between the states correlating to different dissociation limits, while in Br2 and I2, with the usual photon energies e.g. less than 20 eV, nonadiabatic transitions occur only between the states correlating to the same dissociation limits, reflecting the different magnitudes of the spin-orbit interactions.
| Original language | English |
|---|---|
| Pages (from-to) | 703-711 |
| Number of pages | 9 |
| Journal | Bulletin of the Korean Chemical Society |
| Volume | 24 |
| Issue number | 6 |
| Publication status | Published - 2003 Jun 20 |
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Keywords
- Nonadiabatic transition
- Noncrossing-type transition
- Photodissociation
- SOCI method
- Spin-orbit interaction
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Theoretical study on the nonadiabatic transitions in the photodissociation of Cl2, Br2, and I2. / Asano, Yukako; Yabushita, Satoshi.
In: Bulletin of the Korean Chemical Society, Vol. 24, No. 6, 20.06.2003, p. 703-711.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Theoretical study on the nonadiabatic transitions in the photodissociation of Cl2, Br2, and I2
AU - Asano, Yukako
AU - Yabushita, Satoshi
PY - 2003/6/20
Y1 - 2003/6/20
N2 - We have theoretically studied the nonadiabatic transitions among the five lower states with the Ω=1u symmetry (1u(1) to 1u(5)) in the photodissociation of Cl2, Br2, and I2 by using the spin-orbit configuration interaction (SOCI) method and the semiclassical time-dependent coupled Schrödinger equations. From the configuration analyses of the SOCI wavefunctions, we found that the nonadiabatic transition between 1u(2) and 1u(1) is a noncrossing type, while that between 1u(3) and 1u(4) is a crossing type for all the molecules. The behavior of the radial derivative coupling element between 1u(1) and 1u(2) and that between 1u(3) and 1u(4) is analyzed in detail. In Cl2, nonadiabatic transitions can take place even between the states correlating to different dissociation limits, while in Br2 and I2, with the usual photon energies e.g. less than 20 eV, nonadiabatic transitions occur only between the states correlating to the same dissociation limits, reflecting the different magnitudes of the spin-orbit interactions.
AB - We have theoretically studied the nonadiabatic transitions among the five lower states with the Ω=1u symmetry (1u(1) to 1u(5)) in the photodissociation of Cl2, Br2, and I2 by using the spin-orbit configuration interaction (SOCI) method and the semiclassical time-dependent coupled Schrödinger equations. From the configuration analyses of the SOCI wavefunctions, we found that the nonadiabatic transition between 1u(2) and 1u(1) is a noncrossing type, while that between 1u(3) and 1u(4) is a crossing type for all the molecules. The behavior of the radial derivative coupling element between 1u(1) and 1u(2) and that between 1u(3) and 1u(4) is analyzed in detail. In Cl2, nonadiabatic transitions can take place even between the states correlating to different dissociation limits, while in Br2 and I2, with the usual photon energies e.g. less than 20 eV, nonadiabatic transitions occur only between the states correlating to the same dissociation limits, reflecting the different magnitudes of the spin-orbit interactions.
KW - Nonadiabatic transition
KW - Noncrossing-type transition
KW - Photodissociation
KW - SOCI method
KW - Spin-orbit interaction
UR - http://www.scopus.com/inward/record.url?scp=0042066692&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0042066692&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0042066692
VL - 24
SP - 703
EP - 711
JO - Bulletin of the Korean Chemical Society
JF - Bulletin of the Korean Chemical Society
SN - 0253-2964
IS - 6
ER -