Near-IR absorption transition of 3H4 to 3F2 for UCl62- complex in M2ZrCl6 host crystals (M = K+, Rb+, and Cs+): an experimental and theoretical study

Sheng Dai; L. M. Toth; G. D. Del Cul; D. H. Metcalf

doi:10.1016/0301-0104(95)00228-6

Near-IR absorption transition of ³H₄ to ³F₂ for UCl₆^2- complex in M₂ZrCl₆ host crystals (M = K⁺, Rb⁺, and Cs⁺): an experimental and theoretical study

Sheng Dai, L. M. Toth, G. D. Del Cul, D. H. Metcalf

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Abstract

The near-IR electronic transition from ground-state G{cyrillic}₁ of ³H₄ to the excited-state G{cyrillic}₃ of ³F₂ for the UCl₆^2- complex in three M₂ZrCl₆ host crystals (M = K⁺, Rb⁺, and Cs⁺) has been investigated experimentally and theoretically. The vibration frequency of the excited state is found to be sensitive to the alkaline ion substitution and the frequency variation follows the trend predicted by the 'counterion effect'. In contrast to previous studies, the apparent anomaly in the intensity ratio of the two vibronic peaks from the prediction of a Boltzmann distribution relationship is attributed to the vibration frequency difference between the ground and the excited state. This new interpretation is supported by computer simulation of the experimental optical spectra.

Original language	English
Pages (from-to)	271-279
Number of pages	9
Journal	Chemical Physics
Volume	200
Issue number	3
DOIs	https://doi.org/10.1016/0301-0104(95)00228-6
State	Published - Nov 15 1995
Externally published	Yes

Funding

This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under contract DE-AC05-84OR21400 with Martin Marietta Energy Systems. We also thank Dr. R.W. Shaw at ORNL for his valuable comments regarding the manuscript.

Funders	Funder number
Office of Basic Energy Sciences	DE-AC05-84OR21400
U.S. Department of Energy

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title = "Near-IR absorption transition of 3H4 to 3F2 for UCl62- complex in M2ZrCl6 host crystals (M = K+, Rb+, and Cs+): an experimental and theoretical study",

abstract = "The near-IR electronic transition from ground-state G{cyrillic}1 of 3H4 to the excited-state G{cyrillic}3 of 3F2 for the UCl62- complex in three M2ZrCl6 host crystals (M = K+, Rb+, and Cs+) has been investigated experimentally and theoretically. The vibration frequency of the excited state is found to be sensitive to the alkaline ion substitution and the frequency variation follows the trend predicted by the 'counterion effect'. In contrast to previous studies, the apparent anomaly in the intensity ratio of the two vibronic peaks from the prediction of a Boltzmann distribution relationship is attributed to the vibration frequency difference between the ground and the excited state. This new interpretation is supported by computer simulation of the experimental optical spectra.",

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T1 - Near-IR absorption transition of 3H4 to 3F2 for UCl62- complex in M2ZrCl6 host crystals (M = K+, Rb+, and Cs+)

T2 - an experimental and theoretical study

AU - Dai, Sheng

AU - Toth, L. M.

AU - Del Cul, G. D.

AU - Metcalf, D. H.

PY - 1995/11/15

Y1 - 1995/11/15

N2 - The near-IR electronic transition from ground-state G{cyrillic}1 of 3H4 to the excited-state G{cyrillic}3 of 3F2 for the UCl62- complex in three M2ZrCl6 host crystals (M = K+, Rb+, and Cs+) has been investigated experimentally and theoretically. The vibration frequency of the excited state is found to be sensitive to the alkaline ion substitution and the frequency variation follows the trend predicted by the 'counterion effect'. In contrast to previous studies, the apparent anomaly in the intensity ratio of the two vibronic peaks from the prediction of a Boltzmann distribution relationship is attributed to the vibration frequency difference between the ground and the excited state. This new interpretation is supported by computer simulation of the experimental optical spectra.

AB - The near-IR electronic transition from ground-state G{cyrillic}1 of 3H4 to the excited-state G{cyrillic}3 of 3F2 for the UCl62- complex in three M2ZrCl6 host crystals (M = K+, Rb+, and Cs+) has been investigated experimentally and theoretically. The vibration frequency of the excited state is found to be sensitive to the alkaline ion substitution and the frequency variation follows the trend predicted by the 'counterion effect'. In contrast to previous studies, the apparent anomaly in the intensity ratio of the two vibronic peaks from the prediction of a Boltzmann distribution relationship is attributed to the vibration frequency difference between the ground and the excited state. This new interpretation is supported by computer simulation of the experimental optical spectra.

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DO - 10.1016/0301-0104(95)00228-6

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Near-IR absorption transition of ³H₄ to ³F₂ for UCl₆^2- complex in M₂ZrCl₆ host crystals (M = K⁺, Rb⁺, and Cs⁺): an experimental and theoretical study

Abstract

Funding

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