On the Renner-Teller effect and barriers to linearity and dissociation in HCF(Ã 1A″)

Haiyan Fan, Ionela Ionescu, Chris Annesley, Joseph Cummins, Matthew Bowers, Ju Xin, Scott A. Reid

Research output: Contribution to journalArticle

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Abstract

To further investigate the Renner-Teller effect and barriers to linearity and dissociation in the simplest singlet carbene (HCF), we recorded fluorescence excitation spectra of the pure bending transitions 2 0 n with n = 0-7 and the combination bands 1 0 1 2 0 n with n = 1-6 and 2 0 n 3 0 1 with n = 0-3 in the HCF à 1A← -X̃ 1A′ system. The spectra were measured under jet-cooled conditions, using a pulsed-discharge source, and rotationally analyzed to yield precise values for the band origins and rotational constants. The derived Ã-state parameters are in excellent agreement with the predictions of ab initio electronic structure theory. The approach to linearity in the à state is evidenced in a sharp increase in the rotational constant A, as first reported by Kable and co-workers, and a minimum in the vibrational intervals near the 2 7 level. A fit of the vibrational intervals for the pure bending levels yields a barrier to linearity of 6300 ± 270 cm -1 above the vibrationless level. Our observation of the K a′ = 1 level of 1 12 6 places a lower limit on the A state barrier to dissociation of ∼ 8555 cm -1 above the vibrationless level.

Original languageEnglish
Pages (from-to)3732-3738
Number of pages7
JournalJournal of Physical Chemistry A
Volume108
Issue number17
DOIs
Publication statusPublished - Apr 29 2004
Externally publishedYes

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linearity
dissociation
Electronic structure
Fluorescence
intervals
carbenes
electronic structure
fluorescence
predictions
excitation
carbene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Fan, H., Ionescu, I., Annesley, C., Cummins, J., Bowers, M., Xin, J., & Reid, S. A. (2004). On the Renner-Teller effect and barriers to linearity and dissociation in HCF(Ã 1A″). Journal of Physical Chemistry A, 108(17), 3732-3738. https://doi.org/10.1021/jp049828o

On the Renner-Teller effect and barriers to linearity and dissociation in HCF(Ã 1A″). / Fan, Haiyan; Ionescu, Ionela; Annesley, Chris; Cummins, Joseph; Bowers, Matthew; Xin, Ju; Reid, Scott A.

In: Journal of Physical Chemistry A, Vol. 108, No. 17, 29.04.2004, p. 3732-3738.

Research output: Contribution to journalArticle

Fan, H, Ionescu, I, Annesley, C, Cummins, J, Bowers, M, Xin, J & Reid, SA 2004, 'On the Renner-Teller effect and barriers to linearity and dissociation in HCF(Ã 1A″)', Journal of Physical Chemistry A, vol. 108, no. 17, pp. 3732-3738. https://doi.org/10.1021/jp049828o
Fan, Haiyan ; Ionescu, Ionela ; Annesley, Chris ; Cummins, Joseph ; Bowers, Matthew ; Xin, Ju ; Reid, Scott A. / On the Renner-Teller effect and barriers to linearity and dissociation in HCF(Ã 1A″). In: Journal of Physical Chemistry A. 2004 ; Vol. 108, No. 17. pp. 3732-3738.
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