Dissociative photoionization mass spectrometry has been used to measure the PhCO+ appearance energies for several benzoyl compounds. Based on these threshold measurements, an experimental 298 K heat of formation of 738.8 ± 3.3 kJ mol−1 is obtained for the benzoyl cation. The experimental results are supported by high-level ab initio calculations.
McLoughlinR.G. and TraegerJ.C., “A photoionization study of some benzoyl compounds—thermochemistry of [C7H5O]+ formation”, Org. Mass Spectrom.14, 434 (1979). doi: 10.1002/oms.1210140808
2.
LiasS.G.BartmessJ.E.LiebmanJ.F.HolmesJ.L.LevinR.D. and MallardW.G., “Gas-phase ion and neutral thermochemistry”, J. Phys. Chem. Ref. Data17, Suppl. 1 (1988).
3.
BentleyT.W., “Structural effects on the solvolytic reactivity of carboxylic and sulfonic acid chlorides. Comparison with gas phase data for cation formation”, J. Org. Chem.73, 6251 (2008). doi: 10.1021/jo800841g
4.
TraegerJ.C. and McLoughlinR.G., “Absolute heats of formation for gas-phase cations”, J. Am. Chem. Soc.103, 3647 (1981). doi: 10.1021/ja00403a006
5.
TraegerJ.C., “Gas-phase heats of formation for alkylimmonium cations by photoionization mass spectrometry”, J. Phys. Chem. A111, 4643 (2007). doi: 10.1021/jp068697j
6.
JunkesJ.SalpeterE.W. and MilazzoG., Atomic spectra in the vacuum ultraviolet from 2250 to 1100 Å, Part one—Al, C, Cu, Fe, Ge, Hg, Si and H2.Specola Vaticano, Vatican City, Rome, Italy (1965).
7.
FrischM.J.TrucksG.W.SchlegelH.B.ScuseriaG.E.RobbM.A.CheesemanJ.R.MontgomeryJ.A.JrVrevenT.KudinK.N.BurantJ.C.MillamJ.M.IyengarS.S.TomasiJ.BaroneV.MennucciB.CossiM.ScalmaniG.RegaN.PeterssonG.A.NakatsujiH.HadaM.EharaM.ToyotaK.FukudaR.HasegawaJ.IshidaM.NakajimaT.HondaY.KitaoO.NakaiH.KleneM.LiX.KnoxJ.E.HratchianH.P.CrossJ.B.AdamoC.JaramilloJ.GompertsR.StratmannR.E.YazyevO.AustinA.J.CammiR.PomelliC.OchterskiJ.W.AyalaP.Y.MorokumaK.VothG.A.SalvadorP.DannenbergJ.J.ZakrzewskiV.G.DapprichS.DanielsA.D.StrainM.C.FarkasO.MalickD.K.RabuckA.D.RaghavachariK.ForesmanJ. B.OrtizJ.V.CuiQ.BaboulA.G.CliffordS.CioslowskiJ.StefanovB.B.LiuG.LiashenkoA.PiskorzP.KomaromiI.MartinR.L.FoxD.J.KeithT.Al-LahamM.A.PengC.Y.NanayakkaraA.ChallacombeM.GillP.M.W.JohnsonB.ChenW.WongM.W.GonzalezC. and PopleJ.A., GAUSSIAN 03, Revision E.01.Gaussian Inc., Wallingford, CT, USA (2004).
8.
RuscicB.BoggsJ.E.BurcatA.CsászárA.G.DemaisonJ.JanoschekR.MartinJ.M.L.MortonM.L.RossiM.J.StantonJ.F.SzalayP.G.WestmorelandP.R.ZabelF. and BércesT., “IUPAC critical evaluation of thermochemical properties of selected radicals. Part I”, J. Phys. Chem. Ref. Data34, 573 (2005). doi: 10.1063/1.1724828
9.
MerrickJ.P.MoranD. and RadomL., “An evaluation of harmonic vibrational frequency scale factors”, J. Phys. Chem. A111, 11683 (2007). doi: 10.1021/jp073974n
10.
BaerT. and MayerP.M., “Statistical Rice–Ramsperger–Kassel–Marcus quasiequilibrium theory calculations in mass spectrometry”, J. Am. Soc. Mass Spectrom.8, 103 (1997). doi: 10.1016/S1044-0305(96)00212-7
11.
TraegerJ.C. and KompéB.M., in Energetics of organic free radicals, Ed by SimõesJ.A.M.GreenburgA. and LiebmanJ.F.Blackie Academic & Professional, Glasgow, UK (1996).
12.
PedleyJ.B., Thermochemical data and structures of organic compounds, Thermodynamics Research Center: College Station, TX, USA (1994).
13.
LinstromP.J. and MallardW.G., Eds., NIST Chemistry WebBook, NIST Standard Reference Database Number 69, National Institute of Standards and Technology, Gaithersburg, USA (http://webbook.nist.gov).
14.
BartmessJ.E., “Thermodynamics of the electron and the proton”, J. Phys. Chem.98, 6420 (1994). doi: 10.1021/j100076a029
15.
ChaseM.W.DaviesC.A.DowneyJ.R.FruripD.J.McDonaldR.A. and SyverudA.N., “JANAF thermochemical tables, third edition”, J. Phys. Chem. Ref Data14, Suppl. 1 (1985).
16.
ElderJ.F.JrBeynonJ.H. and CooksR.G., “The benzoyl ion. Thermochemistry and kinetic energy release”, Org. Mass Spectrom.11, 415 (1976). doi: 10.1002/oms.1210110414