Potential energy curves of ICl and non-adiabatic interactions studied by the spin-orbit CI method

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Abstract

Excited state potential curves of ICl have been obtained by the spin- orbit CI method to describe the non-adiabatic interactions. Variations of each wavefunction are analyzed and three avoided crossings are characterized between 0+(III)/0+(IV), 0+(II)/0+(IV), and 0+(II)/0+(III) at R = 2.85, 3.14 and 3.62 Å, respectively. The second avoided crossing, that was suggested before by Tiemann et al. is proved here for the first time. Our 1II1, 1(II) state crosses with the B state just inside the second avoided crossing, supporting the experimental analyses made by Gordon et al. and Tiemann et al. Applying to the B state photodissociation, our potential curves yield the wavelength dependence of the branching ratios, I(2P(3/2))+Cl(2P(3/2))/I(2P(3/2))+Cl(2P(1/2)), in good agreement with experimental results. Photodissociation from the second absorption band is also discussed based on our theoretical and recent experimental results.

Original languageEnglish
Pages (from-to)523-532
Number of pages10
JournalJournal of Molecular Structure: THEOCHEM
Volume461-462
DOIs
Publication statusPublished - 1999 Apr 2

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Photodissociation
Orbit
Potential energy
Orbits
potential energy
orbits
photodissociation
curves
Wave functions
Excited states
Absorption spectra
interactions
Wavelength
absorption spectra
wavelengths
excitation

Keywords

  • Avoided crossing
  • Fine structure branching ratio
  • Non-adiabatic interaction
  • Relativistic effective core potential
  • Spin-orbit CI method

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

@article{a9994e1c038c4727b253b93862fb3b50,
title = "Potential energy curves of ICl and non-adiabatic interactions studied by the spin-orbit CI method",
abstract = "Excited state potential curves of ICl have been obtained by the spin- orbit CI method to describe the non-adiabatic interactions. Variations of each wavefunction are analyzed and three avoided crossings are characterized between 0+(III)/0+(IV), 0+(II)/0+(IV), and 0+(II)/0+(III) at R = 2.85, 3.14 and 3.62 {\AA}, respectively. The second avoided crossing, that was suggested before by Tiemann et al. is proved here for the first time. Our 1II1, 1(II) state crosses with the B state just inside the second avoided crossing, supporting the experimental analyses made by Gordon et al. and Tiemann et al. Applying to the B state photodissociation, our potential curves yield the wavelength dependence of the branching ratios, I(2P(3/2))+Cl(2P(3/2))/I(2P(3/2))+Cl(2P(1/2)), in good agreement with experimental results. Photodissociation from the second absorption band is also discussed based on our theoretical and recent experimental results.",
keywords = "Avoided crossing, Fine structure branching ratio, Non-adiabatic interaction, Relativistic effective core potential, Spin-orbit CI method",
author = "Satoshi Yabushita",
year = "1999",
month = "4",
day = "2",
doi = "10.1016/S0166-1280(98)00441-2",
language = "English",
volume = "461-462",
pages = "523--532",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",
publisher = "Elsevier BV",

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TY - JOUR

T1 - Potential energy curves of ICl and non-adiabatic interactions studied by the spin-orbit CI method

AU - Yabushita, Satoshi

PY - 1999/4/2

Y1 - 1999/4/2

N2 - Excited state potential curves of ICl have been obtained by the spin- orbit CI method to describe the non-adiabatic interactions. Variations of each wavefunction are analyzed and three avoided crossings are characterized between 0+(III)/0+(IV), 0+(II)/0+(IV), and 0+(II)/0+(III) at R = 2.85, 3.14 and 3.62 Å, respectively. The second avoided crossing, that was suggested before by Tiemann et al. is proved here for the first time. Our 1II1, 1(II) state crosses with the B state just inside the second avoided crossing, supporting the experimental analyses made by Gordon et al. and Tiemann et al. Applying to the B state photodissociation, our potential curves yield the wavelength dependence of the branching ratios, I(2P(3/2))+Cl(2P(3/2))/I(2P(3/2))+Cl(2P(1/2)), in good agreement with experimental results. Photodissociation from the second absorption band is also discussed based on our theoretical and recent experimental results.

AB - Excited state potential curves of ICl have been obtained by the spin- orbit CI method to describe the non-adiabatic interactions. Variations of each wavefunction are analyzed and three avoided crossings are characterized between 0+(III)/0+(IV), 0+(II)/0+(IV), and 0+(II)/0+(III) at R = 2.85, 3.14 and 3.62 Å, respectively. The second avoided crossing, that was suggested before by Tiemann et al. is proved here for the first time. Our 1II1, 1(II) state crosses with the B state just inside the second avoided crossing, supporting the experimental analyses made by Gordon et al. and Tiemann et al. Applying to the B state photodissociation, our potential curves yield the wavelength dependence of the branching ratios, I(2P(3/2))+Cl(2P(3/2))/I(2P(3/2))+Cl(2P(1/2)), in good agreement with experimental results. Photodissociation from the second absorption band is also discussed based on our theoretical and recent experimental results.

KW - Avoided crossing

KW - Fine structure branching ratio

KW - Non-adiabatic interaction

KW - Relativistic effective core potential

KW - Spin-orbit CI method

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U2 - 10.1016/S0166-1280(98)00441-2

DO - 10.1016/S0166-1280(98)00441-2

M3 - Article

VL - 461-462

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EP - 532

JO - Computational and Theoretical Chemistry

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SN - 2210-271X

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