Determination of the singlet-triplet splitting and electron affinity of o-benzyne by negative ion photoelectron spectroscopy

Leopold, D. G.; Miller, Amy E. Stevens; Lineberger, W. C.

doi:10.1021/ja00267a003

Cited by 120 publications

(113 citation statements)

References 6 publications

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“…With the help of DE ST value one can explain the reactivity of biradicals. It is thus of great importance to be able to calculate DE ST gaps very accurately [27][28][29][30][31][32][33][34][35][36]. The m-benzyne is a challenging diradical system featuring the ground state to be a singlet ( 1 A 1 ) with a monocyclic structure rather than triplet ( 3 B 2 ).…”

Section: Meta-benzynementioning

confidence: 99%

Studies on m-benzyne and phenol via improved virtual orbital-complete active space configuration interaction (IVO-CASCI) analytical gradient method

Chattopadhyay

Chaudhuri

Mahapatra³

2010

Chemical Physics Letters

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Section: Meta-benzynementioning

confidence: 99%

Studies on m-benzyne and phenol via improved virtual orbital-complete active space configuration interaction (IVO-CASCI) analytical gradient method

Chattopadhyay

Chaudhuri

Mahapatra³

2010

Chemical Physics Letters

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“…Distonic radical anions, with separated charge and radical sites [7,8], can be considered as an one-electron reduction product of the corresponding diradical. Gas-phase ion chemistry and negative ion photoelectron spectroscopy (NIPES) have been combined to provide a new method to study diradicals [9][10][11]. One example of a diradical studied in this fashion is tetramethyleneethane (TME).…”

Section: Introductionmentioning

confidence: 99%

Didehydro radical anions from ketones via O− chemical ionization

Lin¹,

Grabowski²

2004

International Journal of Mass Spectrometry

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“…For gas-phase systems, the majority of the reported studies is concerned with the determination of * Corresponding author. electron affinities [3][4][5][6][7][8][9] and the kinetics of electron transfer reactions involving stable radical anions or anions [3,10,11]. Only a limited number of studies have been concerned with the possible occurrence of electron transfer to haloalkanes in the gas phase [12][13][14][15][16][17][18] notwithstanding that special attention has been paid to the interplay between dissociative electron transfer and SN 2 substitution in reactions with 0168-1176/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved SSDI 0168-1176(94)04127-X these compounds in the condensed phase [1,19].…”

Section: Introductionmentioning

confidence: 99%

Formation, stability and structure of radical anions of chloroform, tetrachloromethane and fluorotrichloromethane in the gas phase

Staneke

Groothuis

Ingemann

et al. 1995

International Journal of Mass Spectrometry and Ion Processes

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UvA-DARE is a service provided by the library of the University of Amsterdam (http://dare.uva.nl) UvA-DARE (Digital Academic Repository)Formation, stability and structure of radical anions of chloroform, tetrachloromethane and fluorotrichloromethane in the gas phase Staneke, P.O.; Groothuis, G.; Ingemann Jorgensen, S.; Nibbering, N.M.M. Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. AbstractThe gas-phase reactions of the CH2S'-radical anion with chloroform, tetrachloromethane, and fluorotrichloromethane (CXC13; X = H, D, C1 and F) have been studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The primary reactions lead to minor amounts of the molecular radical anions of the halomethanes in addition to CHzSC1-and CI-, which are formed as the major product ions. The initial step is suggested to be electron transfer with formation of a [CHzS q-CXCI;-] ion/molecule complex, which may dissociate to the radical anion of the halomethane or react further to yield a [CH2S + C1-+ CXC1½-] complex prior to the generation of the C1-or CH2SC1-ions. The radical anions of CHC13 and CC14 react with the parent compounds to yield CHC14 and CCI;-ions, respectively, whereas CFClj transfer a C1 ion only to the CHsSH molecules also present in the FT-ICR cell. On the basis of the facile occurrence of CI-transfer, the CXCIs-ions are proposed to exist in a structure which can be described as a chloride ion weakly bonded to a CXCI2 radical. The formation of the CXCIs-ions in the reaction with the CHzS'-radical anion places a lower limit of 45kJmo1-1 for the electron affinities of the CXC13 molecules. The occurrence of CI-transfer from the CHCI~ ion to the parent compound leads to an indicated upper limit of 75 kJmo1-1 for the electron affinity of chloroform. Similarly, the occurrence of C1-transfer from the CC1U ion to the parent compound is used to derive an upper limit of 110 kJ mol 1 for the electron affinity of tetrachloromethane. These upper limits suggest that previously reported values overestimate the electron affinities of chloroform and tetrachloromethane.

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Determination of the singlet-triplet splitting and electron affinity of o-benzyne by negative ion photoelectron spectroscopy

Cited by 120 publications

References 6 publications

Studies on m-benzyne and phenol via improved virtual orbital-complete active space configuration interaction (IVO-CASCI) analytical gradient method

Studies on m-benzyne and phenol via improved virtual orbital-complete active space configuration interaction (IVO-CASCI) analytical gradient method

Didehydro radical anions from ketones via O− chemical ionization

Formation, stability and structure of radical anions of chloroform, tetrachloromethane and fluorotrichloromethane in the gas phase

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