Computational study on the mechanism and rate constant for the C 6H5 + C6H5NO reaction

Z. F. Xu, Ming-Chang Lin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The reaction mechanism of C6H5 + C6H 5NO involving four product channels on the doublet-state potential energy surface has been studied at the B3LYP/6-31+G(d, p) level of theory. The first reaction channel occurs by barrierless association forming (C 6H5)2NO (biphenyl nitroxide), which can undergo isomerization and decomposition. The second channel takes place by substitution reaction producing C12H10 (biphenyl) and NO. The third and fourth channels involve direct hydrogen abstraction reactions producing C6H4NO + C6H6 and C 6H5NOH + C6H4, respectively. Bimolecular rate constants of the above four product channels have been calculated in the temperature range 300-2000 K by the microcanonical Rice-Ramsperger-Kassel-Marcus theory and/or variational transition-state theory. The result shows the dominant reactions are channel 1 at lower temperatures (T < 800 K) and channel 3 at higher temperatures (T > 800 K). The total rate constant at 7 Torr He is predicted to be kt = 3.94 × 10 21 T-3.09 exp(-699/T) for 300-500 K, 2.09 × 10 20 T-3.56 exp(2315/T) for 500-1000 K, and 1.51 × 102 T3.30 exp(-3043/T) for 1000-2000 K (in units of cm3 mol-1 s-1), agreeing reasonably with the experimental data within their reported errors. The heats of formation of key products including biphenyl nitroxide, hydroxyl phenyl amino radical, and N-hydroxyl carbazole have been estimated.

Original languageEnglish
Pages (from-to)9054-9060
Number of pages7
JournalJournal of Physical Chemistry A
Volume109
Issue number40
DOIs
StatePublished - 13 Oct 2005

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