Electronic spectroscopy of the à 1A″ ← X̃ 1A′ system of CDF

Chong Tao, Mihaela Deselnicu, Haiyan Fan, Calvin Mukarakate, Ionela Ionescu, Scott A. Reid

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

To further investigate the Renner-Teller (RT) effect and barriers to linearity and dissociation in the simplest singlet carbene, we recorded fluorescence excitation spectra of bands involving the pure bending levels 2n0 with n = 0-9 and the combination states 1102n0 with n = 1-8 and 2n0310 with n = 0-5 in the à 1A″ ← X̃ 1A′ system of CDF, in addition to some weak hot bands. 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; fluorescence lifetimes were also measured to probe for lifetime lengthening effects due to the RT interaction. The derived à state parameters are compared with previous results for CHF and with predictions of ab initio electronic structure theory. The approach to linearity in the à state is evidenced in a sharp increase in the A rotational constant with bending excitation, and a minimum in the vibrational intervals near 29. A fit of the vibrational intervals for the pure bending levels yields an à state barrier to linearity in good agreement both with that previously derived for CHF and ab initio predictions. From the spectra and lifetime measurements, the onset of extensive RT perturbations is found to occur at a higher energy than in CHF, consistent with the smaller A constant.

Original languageEnglish
Pages (from-to)707-713
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume8
Issue number6
DOIs
Publication statusPublished - 2006
Externally publishedYes

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linearity
Fluorescence
Spectroscopy
life (durability)
electronics
spectroscopy
Electronic structure
intervals
fluorescence
carbenes
predictions
excitation
dissociation
electronic structure
perturbation
probes
interactions
energy
carbene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Electronic spectroscopy of the à 1A″ ← X̃ 1A′ system of CDF. / Tao, Chong; Deselnicu, Mihaela; Fan, Haiyan; Mukarakate, Calvin; Ionescu, Ionela; Reid, Scott A.

In: Physical Chemistry Chemical Physics, Vol. 8, No. 6, 2006, p. 707-713.

Research output: Contribution to journalArticle

Tao, C, Deselnicu, M, Fan, H, Mukarakate, C, Ionescu, I & Reid, SA 2006, 'Electronic spectroscopy of the à 1A″ ← X̃ 1A′ system of CDF', Physical Chemistry Chemical Physics, vol. 8, no. 6, pp. 707-713. https://doi.org/10.1039/b514826j
Tao, Chong ; Deselnicu, Mihaela ; Fan, Haiyan ; Mukarakate, Calvin ; Ionescu, Ionela ; Reid, Scott A. / Electronic spectroscopy of the à 1A″ ← X̃ 1A′ system of CDF. In: Physical Chemistry Chemical Physics. 2006 ; Vol. 8, No. 6. pp. 707-713.
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