Electron-transfer reactions between hydrocarbon dications and neutral hydrocarbons lead to an unequal deposition of the excess energy from the reaction in the pair of monocations formed. The initial observation of this phenomenon was explained by the different states accessible upon single-electron capture by a dication compared to single-electron ejection from a neutral compound. Alternatively, however, isomeric structures of the dicationic species, pronounced Franck–Condon effects, as well as excess energy in the dicationic precursors could cause the asymmetric energy partitioning in such dication/neutral collisions. Here, the investigation of this phenomenon in an interdisciplinary cooperation is described, shedding light not only upon a possible solution to the problem at hand, but also providing an example for the synergistic benefits of international research networks applying complementary approaches.
TerlouwJ.K.SchwarzH., “The generation and characterization of molecules by neutralization–reionization mass spectrometry (NRMS)”, Angew. Chem. Int. Ed. Engl.26, 805 (1987). doi: 10.1002/anie.198708053
HopC.E.C.A., “Mass spectrometric experiments with beams of fast neutrals”, PhD thesis, University of Utrecht, Utrecht, The Netherlands (1988).
4.
PetrieS.JavaheryG.WincelH.BohmeD.K., “Proton-transfer from a fullerene dication—Bracketing of the gas-phase acidity of C60H2+”, J. Am. Chem. Soc.115, 6290 (1993). doi: 10.1021/ja00067a050
5.
SchröderD.SchwarzH., “Generation, stability, and reactivity of small, multiply charged ions in the gas phase”, J. Phys. Chem. A103, 7385 (1999). doi: 10.1021/jp991332x
6.
SchröderD., “Coulomb explosions and more of multiply charged ions”, Angew. Chem. Int. Ed.43, 1329 (2004). doi: 10.1002/anie.200301728
7.
PriceS.D., “Coincidence studies of the bond-forming reactivity and reaction dynamics of molecular dications”, Int. J. Mass Spectrom.260, 1 (2007). doi: 10.1016/j.ijms.2006.06.018
8.
BoxfordW.E.DessentC.E.H., “Probing the intrinsic features and environmental stabilization of multiply charged anions”, Phys. Chem. Chem. Phys.8, 5151 (2006). doi: 10.1039/b609123g
9.
PriceS.D.RoithováJ., “Multiply charged ions in the gas phase”, Phys. Chem. Chem. Phys.13, 18251 (2011). doi: 10.1039/c1cp90163j
10.
BohmeD.K., “Buckminsterfullere cations: New dimensions in gas-phase ion chemistry”, Mass Spectrom. Rev.28, 672 (2009). doi: 10.1002/mas.20227
PaulingL., “The normal state of the helium moleculeions He2+ and He2++”, J. Chem. Phys.1, 56 (1933). doi: 10.1063/1.1749219
13.
ScheierP., “Multiply charged ions”, in Encyclopedia of Mass Spectrometry, Vol. 1, Ed by ArmentroutP.B., Elsevier, Amsterdam, The Netherlands, p. 455 (2003).
14.
PriceS.D.ManningM.LeoneS.R., “Bond-forming reactions of gas-phase molecular dications”, J. Am. Chem. Soc.116, 8673 (1994). doi: 10.1021/ja00098a030
15.
PriceS.D., “Investigating the gas-phase chemical reactions of molecular dications”, Phys. Chem. Chem. Phys.5, 1717 (2003). doi: 10.1039/b301957h
RoithováJ.SchröderD., “Bimolecular reactions of molecular dications: New reactivity paradigms and bond-forming processes”, Phys. Chem. Chem. Phys.9, 2341 (2007). doi: 10.1039/b617681j
18.
RoithováJ., “Superelectrophilic chemistry in the gas phase”, Pure Appl. Chem.83, 1499 (2011). doi: 10.1351/PAC-CON-10-10-17
19.
HermanZ., “Dynamics of charge transfer and chemical reactions of doubly charged ions at low collision energies”, Int. Rev. Phys. Chem.15, 299 (1996). doi: 10.1080/01442359609353186
RoithováJ.HermanZ.SchröderD.SchwarzH., “Competition of proton and electron transfers in gas-phase reactions of hydrogen-containing dications CHX2+ (X = F, Cl, Br, I) with atoms, nonpolar and polar molecules”, Chem. Eur. J.12, 2465 (2006). doi: 10.1002/chem.200500888
RickettsC.L.SchröderD.AlcarazC.RoithováJ., “Growth of larger hydrocarbon ions in the ionosphere of Titan”, Chem. Eur. J.14, 4779 (2008). doi: 10.1002/chem.200800524
24.
AscenziD.RoithováJ.SchröderD.ZinsE.-L.AlcarazC., “Growth of doubly ionized C,H,N compounds in the presence of methane”, J. Phys. Chem. A113, 11204 (2009). doi: 10.1021/jp904859g
25.
ZinsE.L.SchröderD., “Carbon–carbon coupling reactions of medium-sized N-containing dications”, J. Phys. Chem. A114, 5989 (2010). doi: 10.1021/jp100852q
26.
ZinsE.-L.SchröderD., “Influence of the structure of medium-sized aromatic precursors on the reactivity of their dications towards rare gases”, Int. J. Mass Spectrom.299, 53 (2011). doi: 10.1016/j.ijms.2010.09.017
27.
RoithováJ.SchröderD., “Bond-forming reactions of molecular dications as a new route to polyaromatic hydrocarbons”, J. Am. Chem. Soc.128, 4208 (2006). doi: 10.1021/ja0600429
28.
RoithováJ.SchröderD., “On the growth mechanism of polycyclic aromatic hydrocarbon dications: C7H62+ + C2H2”, Chem. Eur. J.13, 2893 (2007). doi: 10.1002/chem.200600913
29.
RoithováJ.RickettsC.L.SchröderD., “Reactions of the dications C7H62+, C7H72+, and C7H82+ with methane: Predominance of doubly charged intermediates”, Int. J. Mass Spectrom.280, 32 (2009). doi: 10.1016/j.ijms.2008.07.017
30.
ZinsE.-L.MilkoP.SchröderD.AysinaJ.AscenziD.ŽabkaJ.AlcarazC.PriceS.D.RoithováJ., “Formation of organo-xenon dications in the reactions of xenon with dications derived from toluene”, Chem. Eur. J.17, 4012 (2011). doi: 10.1002/chem.201002556
31.
AscenziD.AysinaJ.ZinsE.-L.SchröderD.ŽabkaJ.AlcarazC.PriceS.D.RoithováJ., “Double ionization of cycloheptatriene and the reactions of the resulting C7H2n+ dications (n = 6, 8) with xenon”, Phys. Chem. Chem. Phys.13, 18330 (2011). doi: 10.1039/c1cp21634a
32.
RoithováJ.SchröderD., “Bond-formation versus electron transfer: C–C coupling reactions of hydrocarbon dications with benzene”, Phys. Chem. Chem. Phys.9, 731 (2007). doi: 10.1039/b615648g
33.
DiauE.W.G.HerekJ.L.KimZ.H.ZewailA.H., “Femtosecond activation of reactions and the concept of nonergodic molecules”, Science279, 847 (1998). doi: 10.1126/science.279.5352.847
34.
SchwarzH., “On the spin-forbiddeness of gas-phase ion–molecules reactions: A fruitful intersection of experimental and computational studies”, Int. J. Mass Spectrom.237, 75 (2004). doi: 10.1016/j.ijms.2004.06.006
35.
HolmesJ.L.TerlouwJ.K.BurgersPC.RyeR.T.B., “Charge stripping mass-spectra: A method for identifying isomeric [C5H8]+• and [C3H6]+• ions”, Org. Mass Spectrom.15, 149 (1980). doi: 10.1002/oms.1210150310
36.
Krogh-JespersenK., “Ab initio electronic-structure calculations on the benzene dication and other C6H62+ isomers”, J. Am. Chem. Soc.113, 417 (1991). doi: 10.1021/ja00002a006
37.
BartmessJ.E., “Gas-phase ion chemistry of 5-methylene-1,3-cyclohexadiene (ortho-isotoluene) and 3- methylene-1,4-cyclohexadiene (para-isotoluene)”, J. Am. Chem. Soc.104, 335 (1982). doi: 10.1021/ja00365a082
38.
ChoeJ.C., “Dissociation of toluene cation: A new potential energy surface”, J. Phys. Chem. A110, 7655 (2006). doi: 10.1021/jp0612782
39.
RoithováJ.SchröderD.GrueneP.WeiskeT.SchwarzH., “Structure of long-lived C7H28+ dications generated by electron ionization of neutral toluene”, J. Phys. Chem. A110, 2970 (2006). doi: 10.1021/jp0545288
40.
HeinemannC.SchröderD.SchwarzH., “Generation of the thermochemically stable dications AlF2+ and SiF2+ via charge-stripping mass spectrometry”, J. Phys. Chem.99, 16195 (1995). doi: 10.1021/j100044a001
41.
RoithováJ.SchröderD., “Silicon compounds of neon and argon”, Angew. Chem. Int. Ed.48, 8788 (2009). doi: 10.1002/anie.200903706
42.
LockyearJ.F.ParkesM.A.PriceS.D., “Fast and efficient fluorination of small molecules by SF42+”, Angew. Chem. Int. Ed.50, 1322 (2011). doi: 10.1002/anie.201006486
43.
SchröderD.SchwarzH.ClemmerD.E.ChenY.-M.ArmentroutPB.BaranovV.I.BöhmeD.K., “Activation of hydrogen and methane by thermalized FeO+ in the gas phase as studied by multiple mass-spectrometric techniques”, Int. J. Mass Spectrom. Ion Processes161, 177 (1997).
44.
Jagoda-CwiklikB.JungwirthP.RulíšekL.MilkoP.RoithováJ.LemaireJ.MaitreP.OrtegaJ.M.SchröderD., “Micro-hydration of the MgNO3+ cation in the gas phase”, ChemPhysChem8, 1629 (2007). doi: 10.1002/cphc.200700196
45.
RoithováJ.MilkoP.RickettsC.L.SchröderD.BessonT.DekojV.BelohradskýM., “Dissociation reactions of free tetrapyridinium tetracations and of their catenanes”, J. Am. Chem. Soc.129, 10141 (2007). doi: 10.1021/ja071058h
46.
HermanZ., “The crossed-beam scattering method in studies of ion–molecule reaction dynamics”, Int. J. Mass Spectrom.212, 413 (2001). doi: 10.1016/S1387-3806(01)00493-6
47.
LockyearJ.F.ParkesM.A.PriceS.D., “Single-electron transfer between Ar2+ (3P, 1D) and He at low collision energies”, J. Phys. B: At. Mol. Opt. Phys.42, 145201 (2009). doi: 10.1088/0953-4075/42/14/145201
48.
RoithováJ.SchröderD., “Reactive monitoring with synchrotron radiation as a unique source of accurate benchmark data for gas-phase reactions”, Chem. Listy103, 636 (2009).
49.
SchröderD.SchalleyC.A.HarveyJ.N.SchwarzH., “On the formation of the carbon dioxide anion radical CO2−• in the gas phase”, Int. J. Mass Spectrom.185–187, 25 (1999).
50.
HogreveH., “Stability properties of CO2+”, J. Phys. B28, L263 (1995). doi: 10.1088/0953-4075/28/8/001
51.
PolakR.HochlafM.LevinasM.ChambaudG.RosmusP., “On the potential energy functions of the electronic states of CO2+”, Spectrochim. Acta A55, 447 (1999). doi: 10.1016/S1386-1425(98)00253-4
52.
JalboutA.F., “High-level ab initio and density functional theory calculations of the dissociation energies, ionization energies, geometrical variations, and vibrational modes of ground and excited CO2, CO+2, and CO22+”, Int. J. Quantum Chem.86, 541 (2002). doi: 10.1002/qua.10020
53.
HochlafM.BennettF.R.ChambaudG.RosmusP., “Theoretical study of the electronic states of CO2++”, J. Phys. B31, (1998) 2163. doi: 10.1088/0953-4075/31/10/007
54.
NIST Chemistry WebBook, National Institute of Standards and Technology, Gaithersburg, USA, 2003. See: http://webbook.nist.gov
55.
SlatteryA.E.FieldT.A.AhmadM.HallR.I.LambourneJ.PenentF.LablanquieP.ElandJ.H.D.“Spectroscopy and metastability of CO22+ molecular ions”, J. Chem. Phys.122, 084317 (2005). doi: 10.1063/1.1850895
56.
HolmesJ.L.JobstK.J.TerlouwJ.K., “Isotopic labelling in mass spectrometry as a tool for studying mechanisms of ion dissociations”, J. Labelled Compd. Radiopharm.50, 1115 (2007). doi: 10.1002/jlcr.1386
57.
RoithováJ.RickettsC.L.SchröderD.PriceS.D., “Bond formation with maintenance of twofold charge: Generation of C2O32+ in the reaction of CO22+ with neutral CO2”, Angew. Chem. Int. Ed.46, (2007) 9316. doi: 10.1002/anie.200704286
58.
FranceschiP.ThissenR.ŽabkaJ.RoithováJ.HermanZ.DutuitO., “Internal energy effects in the reactivity of CO22+ doubly charged molecular ions with CO2 and CO”, Int. J. Mass Spectrom.228, 507 (2003). doi: 10.1016/S1387-3806(03)00157-X
59.
RickettsC.L.SchröderD.RoithováJ.SchwarzH.ThissenR.DutuitO.ŽabkaJ.HermanZ.PriceS.D., “Competition of electron transfer, dissociation, and bond-forming reactions in collisions of CO22+ with neutral CO2”, Phys. Chem. Chem. Phys.10, 5135 (2008). doi: 10.1039/b800865e
60.
ŽabkaJ.RickettsC.L.SchröderD.RoithováJ.SchwarzH.ThissenR.DutuitO.PriceS.D.HermanZ., “Crossed-beam scattering studies of electron-transfer processes between the dication CO22+ and neutral CO2: Electronic states of reactants and products involved”, J. Phys. Chem. A114, 6463 (2010). doi: 10.1021/jp1023795
FeixasF.PonecR.SchröderD.RoithováJ.FišerJ.PriceS.D., “Bonding analysis of the [C2O4]2+ intermediate formed in the reaction of CO22+ with neutral CO2”, J. Phys. Chem. A114, 6681 (2010). doi: 10.1021/jp1020559
63.
HuW.-P.HarperS.M.PriceS.D., “A position-sensitive coincidence spectrometer to image the kinematics of the bimolecular reactions of molecular dications”, Meas. Sci. Technol.13, 1512 (2002). doi: 10.1088/0957-0233/13/10/302
64.
ParkesM.A.LockyearJ.F.SchröderD.RoithováJ.PriceS.D., “Electronic state selectivity in dication–molecule single electron transfer reactions: NO2+ + NO”, Phys. Chem. Chem. Phys.13, 18386 (2011). doi: 10.1039/c1cp21612k
SchröderD.LoosJ.SchwarzH.ThissenR.DutuitO.MourguesP.AudierH.-E., “Barrier height titration by tunable photoionization with chemical monitoring: Unimolecular keto/enol tautomerism of the acetamide cation radical”, Angew. Chem. Int. Ed.41, 2748 (2002). doi: 10.1002/1521-3773(20020802)41:15<2748::AID-ANIE2748>3.0.CO;2-V
67.
AlcarazC.NicolasC.ThissenR.ŽabkaJ.DutuitO., “15N+ + CD4 and O+ + 13CO2 state-selected ion–molecule reactions relevant to the chemistry of planetary ionospheres”, J. Phys. Chem. A108, 9998 (2004). doi: 10.1021/jp0477755
68.
SchröderD.LoosJ.SchwarzH.ThissenR.DutuitO., “Protonated benzene: A case for structural memory effects?”, J. Phys. Chem. A108, 9931 (2004). doi: 10.1021/jp0479973
69.
SchröderD.LoosJ.EngeserM.SchwarzH.JankowiakC.BergerR.ThissenR.DutuitO.DöblerJ.SauerJ., “Ion chemistry of OV(OCH3)3: Molecular ions and primary fragmentations”, Inorg. Chem.43, 1976 (2004).
70.
RoithováJ.SchröderD.LoosJ.SchwarzH.JankowiakH.C.BergerR.ThissenR.DutuitO., “Revision of the second ionization energy of toluene”, J. Chem. Phys.122, 094306 (2005). doi: 10.1063/1.1856916
ShafferC.SchröderD.ZinsE.-L.AlcarazC.ŽabkaJ.RoithováJ., “Unimolecular dissociation of doubly ionized toluene and electron transfer between neutral toluene and its dication”, Chem. Phys. Lett.534, 8 (2012). doi: 10.1016/j.cplett.2012.03.014
