Theoretical study on the nonadiabatic transitions in the photodissociation of Cl2, Br2, and I2

Yukako Asano, Satoshi Yabushita

Research output: Contribution to journalArticle

9 Citations (Scopus)

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 languageEnglish
Pages (from-to)703-711
Number of pages9
JournalBulletin of the Korean Chemical Society
Volume24
Issue number6
Publication statusPublished - 2003 Jun 20

Fingerprint

Photodissociation
Orbits
Wave functions
Photons
Derivatives
Molecules

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 journalArticle

@article{42e0d24576ff4f55846d710c77c49448,
title = "Theoretical study on the nonadiabatic transitions in the photodissociation of Cl2, Br2, and I2",
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 Schr{\"o}dinger 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.",
keywords = "Nonadiabatic transition, Noncrossing-type transition, Photodissociation, SOCI method, Spin-orbit interaction",
author = "Yukako Asano and Satoshi Yabushita",
year = "2003",
month = "6",
day = "20",
language = "English",
volume = "24",
pages = "703--711",
journal = "Bulletin of the Korean Chemical Society",
issn = "0253-2964",
publisher = "Korean Chemical Society",
number = "6",

}

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 -