Theoretical study on the photoabsorption in the Herzberg I band system of the O2 molecule

Ryuta Takegami, Satoshi Yabushita

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The Herzberg I band system of the oxygen molecule is electric-dipole forbidden and its absorption strength has been explained by intensity borrowing models which include the spin-orbit (SO) and L-uncoupling (RO) interactions as perturbations. We employed three different levels of theoretical models to evaluate these two interactions, and obtained the rotational and vibronic absorption strengths using the ab initio method. The first model calculates the transition moments induced by the SO interaction variationally with the SO configuration interaction method (SOCI), and uses the first-order perturbation theory for the RO interaction, and is called SOCI. The second is based on the first-order perturbation theory for both the SO and RO interactions, and is called Pert (Full). The last is a limited version of Pert(Full), in that the first-order perturbation wavefunction for the initial and final state is represented by only one dominant basis, namely the 13Πg and B3Σu- state, respectively, as originally used by England et al. [Can. J. Phys. 74 (1996) 185], and is called Pert(England). The vibronic oscillator strengths calculated by these three models were in good agreement with the experimental values. As for the integrated rotational linestrengths, the SOCI and Pert(Full) models reproduced the experimental results very well, however the Pert(England) model did not give satisfactory results. Since the Pert(England) model takes only the 1 3Πg and B3Σu- states into consideration, it cannot contain the complicated configuration interactions with highly excited states induced by the SO and RO interaction, which plays an important role for calculating the delicate integrated rotational linestrength. This result suggests that the configuration interaction with highly excited states due to some perturbations cannot be neglected in the case of very weak absorption band systems.

Original languageEnglish
Pages (from-to)63-77
Number of pages15
JournalJournal of Molecular Spectroscopy
Volume229
Issue number1
DOIs
Publication statusPublished - 2005 Jan

Fingerprint

photoabsorption
configuration interaction
Molecules
Orbits
England
molecules
orbits
Excited states
perturbation
interactions
perturbation theory
Wave functions
spin-orbit interactions
oscillator strengths
electric dipoles
excitation
Absorption spectra
Oxygen
absorption spectra
moments

Keywords

  • Electric-dipole forbidden band system
  • Herzberg band system
  • L-uncoupling
  • Rotational linestrength
  • Spin-orbit coupling
  • Vibronic oscillator strength

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Theoretical study on the photoabsorption in the Herzberg I band system of the O2 molecule. / Takegami, Ryuta; Yabushita, Satoshi.

In: Journal of Molecular Spectroscopy, Vol. 229, No. 1, 01.2005, p. 63-77.

Research output: Contribution to journalArticle

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abstract = "The Herzberg I band system of the oxygen molecule is electric-dipole forbidden and its absorption strength has been explained by intensity borrowing models which include the spin-orbit (SO) and L-uncoupling (RO) interactions as perturbations. We employed three different levels of theoretical models to evaluate these two interactions, and obtained the rotational and vibronic absorption strengths using the ab initio method. The first model calculates the transition moments induced by the SO interaction variationally with the SO configuration interaction method (SOCI), and uses the first-order perturbation theory for the RO interaction, and is called SOCI. The second is based on the first-order perturbation theory for both the SO and RO interactions, and is called Pert (Full). The last is a limited version of Pert(Full), in that the first-order perturbation wavefunction for the initial and final state is represented by only one dominant basis, namely the 13Πg and B3Σu- state, respectively, as originally used by England et al. [Can. J. Phys. 74 (1996) 185], and is called Pert(England). The vibronic oscillator strengths calculated by these three models were in good agreement with the experimental values. As for the integrated rotational linestrengths, the SOCI and Pert(Full) models reproduced the experimental results very well, however the Pert(England) model did not give satisfactory results. Since the Pert(England) model takes only the 1 3Πg and B3Σu- states into consideration, it cannot contain the complicated configuration interactions with highly excited states induced by the SO and RO interaction, which plays an important role for calculating the delicate integrated rotational linestrength. This result suggests that the configuration interaction with highly excited states due to some perturbations cannot be neglected in the case of very weak absorption band systems.",
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AB - The Herzberg I band system of the oxygen molecule is electric-dipole forbidden and its absorption strength has been explained by intensity borrowing models which include the spin-orbit (SO) and L-uncoupling (RO) interactions as perturbations. We employed three different levels of theoretical models to evaluate these two interactions, and obtained the rotational and vibronic absorption strengths using the ab initio method. The first model calculates the transition moments induced by the SO interaction variationally with the SO configuration interaction method (SOCI), and uses the first-order perturbation theory for the RO interaction, and is called SOCI. The second is based on the first-order perturbation theory for both the SO and RO interactions, and is called Pert (Full). The last is a limited version of Pert(Full), in that the first-order perturbation wavefunction for the initial and final state is represented by only one dominant basis, namely the 13Πg and B3Σu- state, respectively, as originally used by England et al. [Can. J. Phys. 74 (1996) 185], and is called Pert(England). The vibronic oscillator strengths calculated by these three models were in good agreement with the experimental values. As for the integrated rotational linestrengths, the SOCI and Pert(Full) models reproduced the experimental results very well, however the Pert(England) model did not give satisfactory results. Since the Pert(England) model takes only the 1 3Πg and B3Σu- states into consideration, it cannot contain the complicated configuration interactions with highly excited states induced by the SO and RO interaction, which plays an important role for calculating the delicate integrated rotational linestrength. This result suggests that the configuration interaction with highly excited states due to some perturbations cannot be neglected in the case of very weak absorption band systems.

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