Distribution of vibrational states of CO2 in the reaction O(1D) + CO2 from time-resolved fourier transform infrared emission spectra

Hui Fen Chen, Hung Chu Chiang, Hiroyuki Matsui, Soji Tsuchiya*, Yuan-Pern Lee

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations


A mixture of O3 and CO2 was irradiated with light from a KrF laser at 248 nm; time-resolved infrared emission of CO2 in the region 2000-2400 cm-1 was observed with a Fourier transform spectrometer. This emission involves one quantum in the asymmetric stretching mode (v3) of CO2 in highly vibrationally excited states. The band contour agrees satisfactorily with a band shape calculated based on a simplified polyad model of CO2 and a vibrational distribution estimated through a statistical partitioning of energy of ∼13 000 cm -1, ∼3100 cm-1 smaller than the available energy, into the vibrational modes of CO2. From this model, approximately 44% and 5% of the available energy of O(1D) + CO2 is converted into the vibrational and rotational energy of product CO2, respectively, consistent with previous reports of ∼50% for the translational energy. An extent of rotational excitation of CO2 much smaller than that expected from statistical calculations indicates a mechanism that causes a small torque to be given to CO2 when an O atom leaves the complex CO3 on the triplet exit surface of potential energy, consistent with quantum-chemical calculations.

Original languageEnglish
Pages (from-to)3431-3437
Number of pages7
JournalJournal of Physical Chemistry A
Issue number15
StatePublished - 16 Apr 2009

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