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 language | English |
|---|---|
| Pages (from-to) | 3732-3738 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry A |
| Volume | 108 |
| Issue number | 17 |
| DOIs | |
| Publication status | Published - Apr 29 2004 |
| Externally published | Yes |
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- Physical and Theoretical Chemistry
Cite this
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 journal › Article
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TY - JOUR
T1 - On the Renner-Teller effect and barriers to linearity and dissociation in HCF(Ã 1A″)
AU - Fan, Haiyan
AU - Ionescu, Ionela
AU - Annesley, Chris
AU - Cummins, Joseph
AU - Bowers, Matthew
AU - Xin, Ju
AU - Reid, Scott A.
PY - 2004/4/29
Y1 - 2004/4/29
N2 - 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.
AB - 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.
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U2 - 10.1021/jp049828o
DO - 10.1021/jp049828o
M3 - Article
VL - 108
SP - 3732
EP - 3738
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 17
ER -