The Electronic Spectrum of Tellurium Dioxide

Hullah, Daniel F.; Brown, John M.

doi:10.1006/jmsp.1999.8044

Cited by 6 publications

(17 citation statements)

References 7 publications

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“…0.45 eV higher in energy than the position at which the LIF band in Ref. 1 decreases to zero intensity. Clearly, the agreement of the ab initio T vert and T e values with the positions of the observed band maxima and the fitted 0 value ͕and/or the measured ͑0-0͒ band position͖, respectively, cannot be considered as good.…”

Section: Introductionmentioning

confidence: 69%

“…6 do not provide unambiguous support for the assignment of the upper electronic state involved in the LIF spectrum to the 1 B 2 state of TeO 2 , as suggested in Ref. 1. Nevertheless, the basis sets used in Ref.…”

Section: Introductionmentioning

confidence: 84%

“…One main aim of the present investigation is to obtain reliable computed T e and T vert values of the low-lying electronic states of TeO 2 , in order to ascertain the assignment of the upper electronic state involved in the observed LIF spectrum of Ref. 1. In this connection, various levels of calculations, in terms of electron correlation and basis size, were carried out as described, and the trends in the calculated minimum-energy geometrical parameters, harmonic vibrational frequencies, and/or relative electronic energies were examined to assess the reliability of the computed quantities.…”

Section: A Ab Initio Calculations: Generalmentioning

confidence: 99%

“…In Ref. 6, results of complete-active-space self-consistent field ͑CASSCF͒ calculations were reported on the lowest 1 2 , employing the CEP-31G* and RCEP-41G* basis sets for O and Te, respectively. Bending potential energy curves of these electronic states were reported, and their equilibrium geometrical parameters were obtained.…”

Section: Introductionmentioning

confidence: 99%

“…6, we propose to carry out near state-of-the-art ab initio calculations on the low-lying electronic states of TeO 2 in order to clarify the assignment of the upper electronic state of the LIF band reported in Ref. 1. In addition, we also propose to carry out Franck-Condon simulation of the 1 B 2 ←X 1 A 1 absorption spectrum of TeO 2 in order to obtain fingerprint-type identification of the observed LIF spectrum, as we have done previously for the chemiluminescence spectrum of HPCl, 9 the SVL emission spectra of AlNC, 10 the LIF spectrum of GaN 2 , 11 and the SVL emission spectra of PO 2 .…”

Section: Introductionmentioning

confidence: 99%

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Ab initio calculations on low-lying electronic states of TeO2 and Franck-Condon simulation of the (1)1B2←X̃ 1A1 TeO2 absorption spectrum including anharmonicity

Lee

Mok

Chau

et al. 2004

The Journal of Chemical Physics

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Ab initio calculations have been carried out on low-lying singlet and triplet states of TeO 2 at different levels of theory with basis sets of up to the augmented-polarized valence-quintuplequality. Equilibrium geometrical parameters, harmonic vibrational frequencies, and relative electronic energies of the X 1 A 1 , 1 B 1 , 1 B 2 , 1 A 2 , 3 A 1 , 3 B 1 , 3 B 2 , and 3 A 2 states of TeO 2 have been calculated. Potential energy functions ͑PEFs͒ of the X 1 A 1 and the (1) 1 B 2 states were computed at the complete-active-space self-consistent-field multireference configuration interaction level, with a basis set of augmented-polarized valence-quadruple-quality. Franck-Condon factors ͑FCFs͒ for the electronic transition between the X 1 A 1 and (1) 1 B 2 states of TeO 2 were calculated with the above-mentioned ab initio PEFs. The (1) 1 B 2 ←X 1 A 1 absorption spectrum of TeO 2 was simulated employing the computed FCFs, which include Duschinsky rotation and anharmonicity, and compared with the recently published laser-induced fluorescence ͑LIF͒ spectrum of Hullah and Brown ͓J. Mol. Spectrosc. 200, 261 ͑2000͔͒. The ab initio results and spectral simulation reported here confirm the upper electronic state involved in the LIF spectrum to be the (1) 1 B 2 state of TeO 2 and also confirm the vibrational assignments of Hullah and Brown. However, our simulated spectrum suggests that the reported LIF spectrum from 345 to 406 nm represents only a portion of the full (1) 1 B 2 ←X 1 A 1 absorption spectrum of TeO 2 , which extends from ca. 406 to 300 nm. Another dye other than the two used by Hullah and Brown is required to cover the 345-300 nm region of the LIF band. Ab initio calculations show strong configuration mixing of the (1) 1 B 2 electronic surface with higher 1 B 2 states in a region of large TeO bond length (у2.0 Å) and OTeO bond angle (у135.0°).

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Section: Introductionmentioning

confidence: 69%

Section: Introductionmentioning

confidence: 84%

Section: A Ab Initio Calculations: Generalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%