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Issue 2, 2001
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Mechanism of TMPD photolysis in alcohols. Spin-dependent ion recombination and photoconductivity

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Abstract

Photolysis of N,N,N′,N′-tetramethyl-1,4-phenylenediamine (TMPD) in liquid alcohols was studied by means of a time-resolved transient conductivity technique and the influence of an external magnetic field. We have shown that no single-photon ionization of TMPD occurs at energies up to 5.5 eV. Instead, the observed photocurrent is a result of diffusion assisted ion pair formation [italic v (to differentiate from Times ital nu)]ia quenching of excited 3TMPD* molecules in their triplet state by electron-accepting solutes. Quenching of the singlet excited state 1TMPD*, on the other hand, leads to fast recombining singlet ion pairs with no resulting free ion current. Competition between the two processes is affected by the external magnetic field and is observed as a magnetic field effect on the photocurrent. The rate constants of quenching of the singlet and triplet excited states of TMPD* by acetone in isopropanol were found to be 3.2 × 109 M−1 s−1 and 2.5 × 108 M−1 s−1, respectively. The quantum yield of free ions originating from the 3TMPD* precursor is close to 80% in the absence of magnetic field, while the yield from the 1TMPD* precursor is negligibly small.

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Publication details

The article was received on 25 Sep 2000, accepted on 15 Nov 2000 and first published on 21 Dec 2000


Article type: Paper
DOI: 10.1039/B007777L
Phys. Chem. Chem. Phys., 2001,3, 204-212

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    Mechanism of TMPD photolysis in alcohols. Spin-dependent ion recombination and photoconductivity

    B. Tadjikov and S. Smirnov, Phys. Chem. Chem. Phys., 2001, 3, 204
    DOI: 10.1039/B007777L

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