Dispersed fluorescence spectroscopy of jet-cooled HCF and DCF

Vibrational structure of the X̃ 1A′ state

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

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

We recorded dispersed fluorescence (DF) spectra following excitation of the pure bending levels 20n and the combination states 101 20n and 20n 301 in the à A″1 ← X̃ A′1 system of HCF and DCF. Spectra were measured with a 0.3 m spectrograph equipped with a gated intensified charge coupled device (CCD) detector and obtained under jet-cooled conditions using a pulsed discharge source. The DF spectra reveal rich detail concerning the vibrational structure of the X̃ state up to 10 000 cm-1. For HCF, resonances among the nearly degenerate levels 11 2n, 2n+1 31, and 2n+2 produce a polyadlike structure in the spectrum, and the usual effective spectroscopic Hamiltonian (Dunham expansion) poorly reproduces the experimental term energies. In contrast, this Hamiltonian works well for the term energies of DCF. Density functional calculations of the ground state vibrational frequencies were performed; the results are in excellent agreement with the experimentally derived vibrational parameters. The search for perturbations involving the low-lying ã A″3 state is described.

Original languageEnglish
Article number014314
JournalJournal of Chemical Physics
Volume123
Issue number1
DOIs
Publication statusPublished - 2005
Externally publishedYes

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Hamiltonians
Fluorescence spectroscopy
Fluorescence
fluorescence
Spectrographs
Vibrational spectra
Charge coupled devices
Ground state
spectroscopy
Density functional theory
Detectors
spectrographs
charge coupled devices
perturbation
expansion
ground state
energy
detectors
excitation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Dispersed fluorescence spectroscopy of jet-cooled HCF and DCF : Vibrational structure of the X̃ 1A′ state. / Fan, Haiyan; Mukarakate, Calvin; Deselnicu, Mihaela; Tao, Chong; Reid, Scott A.

In: Journal of Chemical Physics, Vol. 123, No. 1, 014314, 2005.

Research output: Contribution to journalArticle

Fan, Haiyan ; Mukarakate, Calvin ; Deselnicu, Mihaela ; Tao, Chong ; Reid, Scott A. / Dispersed fluorescence spectroscopy of jet-cooled HCF and DCF : Vibrational structure of the X̃ 1A′ state. In: Journal of Chemical Physics. 2005 ; Vol. 123, No. 1.
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