Cyanobenzyl and chlorobenzyl radicals via anion photoelectron imaging spectroscopy

Andrew R. Dixon, Dmitry Khuseynov, Andrei M Sanov

Research output: Contribution to journalArticle

Abstract

We report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 ± 0.01 eV, determined from a combination of the experiment and theory, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. From these results, the C-H bond dissociation energies at the benzyl-α sites of the corresponding closed-shell parent molecules are determined: 80.9 ± 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions and in relation to other similar molecules.

Original languageEnglish (US)
Pages (from-to)72-77
Number of pages6
JournalChemical Physics Letters
Volume614
DOIs
StatePublished - Oct 20 2014

Fingerprint

Photoelectrons
Anions
photoelectrons
Spectroscopy
anions
Imaging techniques
Electron affinity
Nitriles
Molecules
nitriles
electron affinity
spectroscopy
molecules
chlorides
dissociation
Experiments
interactions
energy
benzyl chloride

ASJC Scopus subject areas

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

Cite this

Cyanobenzyl and chlorobenzyl radicals via anion photoelectron imaging spectroscopy. / Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei M.

In: Chemical Physics Letters, Vol. 614, 20.10.2014, p. 72-77.

Research output: Contribution to journalArticle

@article{49ef44e128fe4d9c88ae1b84a7e09bd5,
title = "Cyanobenzyl and chlorobenzyl radicals via anion photoelectron imaging spectroscopy",
abstract = "We report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 ± 0.01 eV, determined from a combination of the experiment and theory, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. From these results, the C-H bond dissociation energies at the benzyl-α sites of the corresponding closed-shell parent molecules are determined: 80.9 ± 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions and in relation to other similar molecules.",
author = "Dixon, {Andrew R.} and Dmitry Khuseynov and Sanov, {Andrei M}",
year = "2014",
month = "10",
day = "20",
doi = "10.1016/j.cplett.2014.09.001",
language = "English (US)",
volume = "614",
pages = "72--77",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Elsevier",

}

TY - JOUR

T1 - Cyanobenzyl and chlorobenzyl radicals via anion photoelectron imaging spectroscopy

AU - Dixon, Andrew R.

AU - Khuseynov, Dmitry

AU - Sanov, Andrei M

PY - 2014/10/20

Y1 - 2014/10/20

N2 - We report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 ± 0.01 eV, determined from a combination of the experiment and theory, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. From these results, the C-H bond dissociation energies at the benzyl-α sites of the corresponding closed-shell parent molecules are determined: 80.9 ± 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions and in relation to other similar molecules.

AB - We report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 ± 0.01 eV, determined from a combination of the experiment and theory, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. From these results, the C-H bond dissociation energies at the benzyl-α sites of the corresponding closed-shell parent molecules are determined: 80.9 ± 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions and in relation to other similar molecules.

UR - http://www.scopus.com/inward/record.url?scp=84907678855&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84907678855&partnerID=8YFLogxK

U2 - 10.1016/j.cplett.2014.09.001

DO - 10.1016/j.cplett.2014.09.001

M3 - Article

AN - SCOPUS:84907678855

VL - 614

SP - 72

EP - 77

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

ER -