An Experimental Test of the Competition Correction for Charge Capture from the Matrix in Intermolecular Electron Tunnelling Reactions

Article abstract of DOI:10.1021/j150642a021

Further experimental tests have been made of a previously presented method to correct for competition for charge capture from the matrix in intermolecular electron transfer (ET) reactions in rigid media.The method is based on a two-step tunnelling model which takes into account the correlation between matrix charge capture and intermolecular electron transfer.The goal is to obtain reliable intermolecular ET rates as a function of distance from measurements on rigid solutions containing two randomly distributed solutes.The method should yield the same rate vs. distance function for different donor solute concentrations.Good agreement was obtained by applying the competition correction to pulse radiolysis data for the reaction of the biphenyl anion with 2-methyl-1,4-naphthoquinone in 2-methyltetrahydrofuran (MTHF) at 77 K for donor:acceptor solute concentration ratios of 20:1 to 2:1.Worse agreement was obtained for the reaction of biphenyl anion with phenanthrene in MTHF, in which case the reaction is slow, and its energetics are substantially influenced by solvation.For such slow reactions, accurate measurements of intermolecular ET rates require donor:acceptor solute concentration ratios such that the donor solute captures most of the matrix charges.It was observed that some biphenyl cations are produced by direct ionizations and are stable in frozen MTHF.

Full text of DOI:10.1021/j150642a021

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.