TY - JOUR
T1 - Potential energy curves of ICl and non-adiabatic interactions studied by the spin-orbit CI method
AU - Yabushita, Satoshi
N1 - Funding Information:
It is a real pleasure to acknowledge Prof. Morokuma's contributions to the whole area of theoretical chemistry. The author would like to thank Profs. Masahiro Kawasaki, Yutaka Matsumi, and Dich N. Zare for the useful discussions on their experimental results. Some calculations were carried out on the SP2 and SX3 at the IMS computer center. This work was supported in part by a Grants-in-Aid for Scientific Research from the Minister of Education, Science, Culture, and Sports of Japan.
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
AN - SCOPUS:0033515407
SN - 2210-271X
VL - 461-462
SP - 523
EP - 532
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
ER -