Restricted accessResearch articleFirst published online 2009-4
Chemistry of (and on) Transition Metal Clusters: A Fourier Transform Ion Cyclotron Resonance Study of the Reaction of Niobium Cluster Cations with Nitric Oxide
The reactions of niobium cluster cations, Nb+n (n = 2–19), with nitric oxide have been investigated using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR). The overall reaction rate constants are found to be in reasonable agreement with collision rates calculated using the surface charge capture model. The dominant reaction for small clusters (n < 9) involves reaction-induced fragmentation resulting in the loss of either NbO or NbN. By contrast, the main reaction observed for the larger clusters (n > 11) is sequential NO chemisorption. Clusters n = 9, 10 exhibit both extremes of behaviour and are the only clusters upon which there is evidence of NO decomposition with N2 loss observed whenever multiple NO molecules are co-adsorbed. The rate constants for each process have been determined as a function of cluster size.
O'HairR.A.J. and KhairallahG.N., “Gas phase ion chemistry of transition metal clusters: Production, reactivity, and catalysis”, J. Cluster Sci.15, 331–363 (2004). doi: 10.1023/B:JOCL.0000041199.40945.e3
2.
ArmentroutP.B., “Reactions and thermochemistry of small transition metal cluster ions”, Annu. Rev. Phys. Chem.52, 423–461 (2001). doi: 10.1146/annurev.physchem.52.1.423
3.
KnickelbeinM.B., “Reactions of transition metal clusters with small molecules”, Annu. Rev. Phys. Chem.50, 79–115 (1999). doi: 10.1146/annurev.physchem.50.1.79
4.
ArmentroutP.B., “The thermochemistry of adsorbates on transition metal cluster ions: Relationship to bulk-phase properties”, Eur. J. Mass Spectrom.9, 531–538 (2003). doi: 10.1255/ejms.585
5.
AndersonM.L.FordM.S.DerrickP.J.DrewelloT.WoodruffD.P. and MackenzieS.R., “Nitric oxide decomposition on small rhodium clusters, Rhn+/–”, J. Phys. Chem. A110, 10992–11000 (2006). doi: 10.1021/jp062178z
6.
HanmuraT.IchihashiM. and KondowT., “Chemisorption of nitrogen monoxide on size-selected cobalt cluster cations”, Isr. J. Chem.47, 37–42 (2007). doi: 10.1560/IJC.47.1.37
7.
AdlhartC. and UggerudE., “C–H activation of alkanes on Rhn+ (n = 1–30) clusters: Size effects on dehydrogenation”, J. Chem. Phys.123, 214709 (2005). doi: 10.1063/1.2131066
8.
BergC.SchindlerT.NiednerschatteburgG. and BondybeyV.E., “Reactions of simple hydrocarbons with Nbn+-chemisorption and physisorption on ionized niobium clusters”, J. Chem. Phys.102, 4870–4884 (1995). doi: 10.1063/1.469535
9.
HardingD.FordM.S.WalshT.R. and MackenzieS.R., “Dramatic size effects and evidence of structural isomers in the reactions of rhodium clusters, Rhn+/–, with nitrous oxide”, Phys. Chem. Chem. Phys.9, 2130–2136 (2007). doi: 10.1039/b618299b
10.
ElkindJ.L.WeissF.D.AlfordJ.M.LaaksonenR.T. and SmalleyR.E., “Fourier-transform ion-cyclotron resonance studies of H2 chemisorption on niobium cluster cations”, J. Chem. Phys.88, 5215–5224 (1988). doi: 10.1063/1.454596
11.
MorseM.D.GeusicM.E.HeathJ.R. and SmalleyR.E., “Surface-reactions of metal-clusters. 2. Reactivity surveys with D2, N2, and CO”, J. Chem. Phys.83, 2293–2304 (1985). doi: 10.1063/1.449321
12.
CoxD.M.ReichmannK.C.TrevorD.J. and KaldorA., “CO chemisorption on free gas-phase metal-clusters”, J. Chem. Phys.88, 111–119 (1988). doi: 10.1063/1.454643
13.
RadiP.P.VonheldenG.HsuM.T.KemperP.R. and BowersM.T., “Thermal bimolecular reactions of size selected transition-metal cluster ions—Nbn+ + O2, n = 1–6”, Int. J. Mass Spectrom. Ion Processes109, 49–73 (1991). doi: 10.1016/0168-1176(91)85096-5
14.
HolmgrenL.AnderssonM. and RosenA., “CO reactivity of small transition-metal clusters—Nin and Nbn”, Surf. Sci.333, 231–236 (1995). doi: 10.1016/0039-6028(95)00099-2
15.
MwakapumbaJ. and ErvinK.N., “Reactivity of niobium cluster anions with nitrogen and carbon monoxide”, Int. J. Mass Spectrom. Ion Processes161, 161–174 (1997). doi: 10.1016/S0168-1176(96)04469-2
16.
WuQ. and YangS., “Reactions of niobium cluster ions Nbn+/– (x = 2–16) with NO and NO2”, Int. J. Mass spectrom.184, 57–65 (1999). doi: 10.1016/S1387-3806(98)14252-5
17.
LohS.K.LianL. and ArmentroutP.B., “Oxidation reactions at variably sized transition-metal centers—Fe+n and Nb+n + O2 (n = 1–3)”, J. Chem. Phys.91, 6148–6163 (1989). doi: 10.1063/1.457434
18.
BercesA.HackettP.A.LianL.MitchellS.A. and RaynerD.M., “Reactivity of niobium clusters with nitrogen and deuterium”, J. Chem. Phys.108, 5476–5490 (1998). doi: 10.1063/1.475936
19.
JiaoC.Q. and FreiserB.S., “Reactions of Nbn+ (n = 2–13) with ethylene in the gas-phase—trends in the kinetics, saturation limits, and degree of dehydrogenation”, J. Phys. Chem.99, 10723–10730 (1995). doi: 10.1021/j100027a008
20.
JiaoC.Q.RanatungaD.R.A. and FreiserB.S., “Reactions of Nbn+ (n = 1–15) with propene and 1-butene: Product distribution as a function of cluster size”, J. Phys. Chem.100, 4755–4759 (1996). doi: 10.1021/jp952303z
21.
BergC.SchindlerT.LammersA.NiednerschatteburgG. and BondybeyV.E., “Dehydrogenation of xylene isomers on niobium cluster cations Nbn+ (n = 2–26)”, J. Phys. Chem.99, 15497–15501 (1995). doi: 10.1021/j100042a025
22.
BergC.BeyerM.AchatzU.JoosS.Niedner-SchatteburgG. and BondybeyV.E., “Effect of charge upon metal cluster chemistry: Reactions of Nbn and Rhn anions and cations with benzene”, J. Chem. Phys.108, 5398–5403 (1998). doi: 10.1063/1.475972
23.
KnickelbeinM.B. and YangS., “Isomers of niobium clusters—direct spectroscopic evidence”, J. Chem. Phys.93, 1476–1477 (1990). doi: 10.1063/1.459159
24.
KnickelbeinM.B. and YangS., “Photoionization studies of niobium clusters—ionization-potentials for Nb2–Nb76”, J. Chem. Phys.93, 5760–5767 (1990). doi: 10.1063/1.459570
25.
LohS.K.LianL. and ArmentroutP.B., “Collision-induced dissociation of niobium cluster ions–transition-metal cluster binding-energies”, J. Am. Chem. Soc.111, 3167–3176 (1989). doi: 10.1021/ja00191a010
26.
HalesD.A.LianL. and ArmentroutP.B., “Collision-induced dissociation of Nbn+ (n = 2–11)—bond-energies and dissociation pathways”, Int. J. Mass Spectrom. Ion Processes102, 269–301 (1990). doi: Doi:10.1016/0168-1176(90)80065-B
27.
BergC.SchindlerT.KantlehnerM.Niedner-SchatteburgG. and BondybeyV.E., “Reactions of homonuclear and heteronuclear group vb clusters with ethylene: Evidence for structural isomers”, Chem. Phys.262, 143–149 (2000). doi: 10.1016/S0301-0104(00)00303-7
28.
ParnisJ.M.Escobar-CabreraE.ThompsonM.G.K.JaculaJ.P.LafleurR.D.Guevara-GarciaA.MartinezA. and RaynerD.M., “Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters”, J. Phys. Chem. A109, 7046–7056 (2005). doi: 10.1021/jp0506944
29.
KietzmannH.MorenzinJ.BechtholdP.S.GanteforG.EberhardtW.YangD.S.HackettP.A.FournierR.PangT. and ChenC.F., “Photoelectron spectra and geometric structures of small niobium cluster anions”, Phys. Rev. Lett.77, 4528–4531 (1996). doi: 10.1103/PhysRevLett.77.4528
30.
MarcyT.P. and LeopoldD.G., “A vibrationally resolved negative ion photoelectron spectrum of Nb8”, Int. J. Mass Spectrom.196, 653–666 (2000). doi: 10.1016/S1387-3806(99)00182-7
31.
FielickeA.RatschC.von HeldenG. and MeijerG., “The far-infrared spectra of neutral and cationic niobium clusters: Nb50/+ to Nb90/+”, J. Chem. Phys.127, 234306 (2007). doi: 10.1063/1.2806176
32.
KumarV. and KawazoeY., “Magnetism in clusters of non-magnetic elements: Pd, Rh, and Ru—magnetism in clusters of non-magnetic elements”, Eur. Phys. J. D, 24, 81–84 (2003). doi: 10.1140/epjd/e2003-00193-6
33.
WalshT.R., “Relaxation dynamics and structural isomerism in Nb10 and Nb+10”, J. Chem. Phys.124, 240317 (2006). doi: 10.1063/1.2201997
34.
GronbeckH. and RosenA., “Investigation of niobium clusters: Bare and co-adsorption”, Phys. Rev. B54, 1549–1552 (1996). doi: 10.1103/PhysRevB.54.1549
35.
GronbeckH.RosenA. and AndreoniW., “Structural, electronic, and vibrational properties of neutral and charged Nbn+ (n = 8,9,10) clusters”, Phys. Rev. A58, 4630–4636 (1998). doi: 10.1103/PhysRevA.58.4630
36.
KumarV. and KawazoeY., “Atomic and electronic structures of niobium clusters”, Phys. Rev. B65, 125403 (2002). doi: 10.1103/PhysRevB.65.125403
37.
BercesA.MitchellS.A. and ZgierskiM.Z., “Reactions between Mn (M = Nb, Mo and n = 1, 2, 3, and 4) and N2. A density functional study”, J. Phys. Chem. A102, 6340–6347 (1998). doi: 10.1021/jp981452p
38.
FordM.S.AndersonM.L.BarrowM.P.WoodruffD.P.DrewelloT.DerrickP.J. and MackenzieS.R., “Reactions of nitric oxide on Rh6+ clusters: Abundant chemistry and evidence of structural isomers”, Phys. Chem. Chem. Phys.7, 975–980 (2005). doi: 10.1039/b415414b
39.
AndersonM.A., “Ion cyclotron resonance studies of the reactions of transition metal clusters with small molecules”, University of Warwick, Coventry, UK (2007).
LeeC.T.YangW.T. and ParrR.G., “Development of the colle-salvetti correlation-energy formula into a functional of the electron-density”, Phys. Rev. B37, 785–789 (1988). doi: 10.1103/PhysRevB.37.785
42.
WadtW.R. and HayP.J., “Ab initio effective core potentials for molecular calculations—potentials for main group elements Na to Bi”, J. Chem. Phys.82, 284–298 (1985). doi: 10.1063/1.448800
43.
FrischM.J.TrucksG.W.SchlegelH.B.ScuseriaG.E.RobbM.A.CheesemanJ.R.MontgomeryJ.VrevenJ.A.T.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.BakkenV.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 b.05.Gaussian Inc., Wallingford, CT, USA (2004).
44.
SchulteM.SchlosserB. and SeidelW., “Ionization gauge sensitivities of N2, O2, N2O, NO, NO2, NH3, CCIF3 and CH3OH”, Fresen. J. Anal. Chem.348, 778–780 (1994). doi: 10.1007/BF00323707
45.
KummerloweG. and BeyerM.K., “Rate estimates for collisions of ionic clusters with neutral reactant molecules”, Int. J. Mass Spectrom.244, 84–90 (2005). doi: 10.1016/j.ijms.2005.03.012
46.
BowersM.T.KemperP.R.von HeldenG. and HsuM.T., Fundamentals of gas phase ion chemistry, Ed by JenningsK.R.Kluwer Academic, New York, USA, p. 55 (1990).
