The time-resolved absorption-detected magnetic resonance spectrum of the polymethylene linked biradical: Effect of the exchange integral

Kiminori Maeda, Yasuyuki Araki, Yoshiyuki Kamata, Kentaro Enjo, Hisao Murai, Tohru Azumi

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

Abstract

The time-resolved absorption-detected magnetic resonance spectrum of the polymethylene linked biradical generated in the photolysis of α-(xanthene-2-carbonyloxy)-ω-(xanthene-2-carbonyloxy)dodecane was observed. The central part of the spectrum shows an increase in the absorbance by applying high microwave power. This is rationalized by the deceleration of the intersystem crossing due to the state locking that serves to slow down the intramolecular recombination reaction. Both wing portions show an increase in the recombination rate by microwave radiation, i.e. acceleration of the intersystem crossing. This is ascribed to transitions from the |T+1〈 and |T+1〈 states to a singlet state having a slight |T0〈 character. We propose that the broadness of the time resolved spectrum is due to the wide distribution of the exchange integral and its fluctuation (modulated exchange integral) by the motion of the polymethylene chain.

Original languageEnglish
Pages (from-to)110-114
Number of pages5
JournalChemical Physics Letters
Volume262
Issue number1-2
DOIs
Publication statusPublished - 1996 Nov 8

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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