Electronic population inversion in HCCO/DCCO products from hyperthermal collisions of O(3P) with HCCH/DCCD

Sridhar A. Lahankar, Jianming Zhang, Sophya Garashchuk, George C Schatz, Timothy K. Minton

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The dynamics of hyperthermal O(3P) reactions with acetylene have been investigated with the use of crossed molecular beams techniques, employing both mass spectrometric and optical detection of products. With collision energies of 40-150 kcal mol-1, O(3P) + HCCH/DCCD → HCCO/DCCO + H/D may follow multiple pathways to form the ketenyl radical (HCCO or DCCO) in ground doublet states or in electronically excited quartet and doublet states. Theoretical calculations support the assignment of the various reaction pathways. The fraction of electronic excitation is substantial. At the highest collision energy studied, ∼65% of the ketenyl radical products that survive are electronically excited, with the majority of the excited products in a quartet state. In this case, a population inversion exists between the electronically excited quartet and ground doublet states of the ketenyl product. Such significant electronic excitation in products is unusual in bimolecular reactions, especially when ground-state products are accessible by spin-allowed pathways.

Original languageEnglish
Pages (from-to)1315-1321
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume4
Issue number8
DOIs
Publication statusPublished - Apr 18 2013

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Dicyclohexylcarbodiimide
population inversion
Ground state
collisions
products
electronics
Acetylene
Molecular beams
ground state
acetylene
molecular beams
excitation
energy

Keywords

  • acetylene
  • hyperthermal atomic oxygen
  • ketenyl radical
  • population inversion

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Electronic population inversion in HCCO/DCCO products from hyperthermal collisions of O(3P) with HCCH/DCCD. / Lahankar, Sridhar A.; Zhang, Jianming; Garashchuk, Sophya; Schatz, George C; Minton, Timothy K.

In: Journal of Physical Chemistry Letters, Vol. 4, No. 8, 18.04.2013, p. 1315-1321.

Research output: Contribution to journalArticle

Lahankar, Sridhar A. ; Zhang, Jianming ; Garashchuk, Sophya ; Schatz, George C ; Minton, Timothy K. / Electronic population inversion in HCCO/DCCO products from hyperthermal collisions of O(3P) with HCCH/DCCD. In: Journal of Physical Chemistry Letters. 2013 ; Vol. 4, No. 8. pp. 1315-1321.
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