Reactions of fourth‐period metal ions (Ca+−Zn+) with O2: Metal‐oxide ion bond energies

Reactions of Ca+, Zn+ and all first‐row atomic transition metal ions with O2 are studied using guided ion beam techniques. While reactions of the ground states of Sc+, Ti+, and V+ are exothermic, the remaining metal ions react with O2 in endothermic processes. Analyses of these endothermic reactions provide new determinations of the M+–O bond energies for these eight elements. Source conditions are varied such that the contributions of excited states of the metal ions can be explicitly considered for Mn+, Co+, Ni+, and Cu+. Results (in eV) at 0 K are D0(Ca+–O)= 3.57±0.05, D0(Cr+–O)=3.72±0.12, D0(Mn+–O)=2.95±0.13, D0(Fe+–O)=3.53±0.06 (reported previously), D0(Co+–O)=3.32±0.06, D0(Ni+–O) =2.74±0.07, D0(Cu+–O)=1.62±0.15, and D0(Zn+–O)=1.65±0.12. These values along with literature data for neutral metal oxide bond energies and ionization energies are critically evaluated. Periodic trends in the ionic metal oxide bond energies are compared with those of the neutral metal oxides and those of other related molec...

[1]  R. Bernstein,et al.  Total Collision Cross Sections for the Interaction of Atomic Beams of Alkali Metals with Gases , 1959 .

[2]  R. Grimley,et al.  Thermodynamics of the Vaporization of Nickel Oxide , 1961 .

[3]  R. Grimley,et al.  Thermodynamics of the Vaporization of Cr2O3: Dissociation Energies of CrO, CrO2, and CrO3 , 1961 .

[4]  J. Drowart,et al.  Vaporization of Compounds and Alloys at High Temperatures. Part 22. Mass Spectrometric Determination of the Dissociation Energy of the Molecules MgO, CaO, SrO and Sr2O , 1963 .

[5]  A. Searcy,et al.  Sublimation and Thermodynamic Properties of Zinc Oxide , 1964 .

[6]  R. W. Kiser,et al.  Ions Produced by Electron Impact with the Dimetallic Carbonyls of Cobalt and Manganese1 , 1965 .

[7]  R. Grimley,et al.  Mass‐Spectrometric Study of the Vaporization of Cobalt Oxide , 1966 .

[8]  R. Marcus.  On the Theory of Chemical‐Reaction Cross Sections. I. A Statistical‐Dynamical Model , 1966 .

[9]  R. F. Barrow,et al.  The Spectroscopy of Diatomic Transition Element Molecules , 1967 .

[10]  G. Distefano.  Photoionization Study of Fe(CO)5 and Ni(CO)4. , 1970, Journal of research of the National Bureau of Standards. Section A, Physics and chemistry.

[11]  G. Balducci,et al.  Dissociation Energy of FeO , 1971 .

[12]  D. Gerlich,et al.  Integral cross sections for ion—molecule reactions. I. The guided beam technique , 1974 .

[13]  D. Hildenbrand.  Thermochemistry of molecular FeO, FeO+ and FeO , 1975 .

[14]  C. Corliss,et al.  Energy Levels of Iron, Fe I through Fe XXVI. Revision, , 1975 .

[15]  J. Rutherford,et al.  Ion–neutral reactions of Al+ with N2, O2, and N2O , 1976 .

[16]  R. K. Sander,et al.  Crossed‐beam chemiluminescent studies of alkaline earth atoms with ClO2 , 1976 .

[17]  E. Murad.  Problems in the chemistry of metallic species in the D and E regions , 1978 .

[18]  M. Bowers,et al.  THEORY OF TRANSLATIONALLY DRIVEN REACTIONS , 1979 .

[19]  P. Dagdigian,et al.  Chemiluminescence from the Ca(4s3d1D)+O2 reaction: Absolute cross sections, photon yield, and CaO dissociation energy , 1980 .

[20]  N. Adams,et al.  Elementary plasma reactions of environmental interest , 1980 .

[21]  L. Halle,et al.  Periodic trends in transition metal-hydrogen, metal-carbon, and metal-oxygen bond dissociation energies. Correlation with reactivity and electronic structure , 1981 .

[22]  M. Kappes,et al.  Oxidation of transition-metal cations in the gas phase. Oxygen bond dissociation energies and formation of an excited-state product , 1981 .

[23]  G. Gigli,et al.  Dissociation energies of the molecules CrPO2(g) and CrO(g) by high-temperature mass spectrometry , 1981 .

[24]  L. Halle,et al.  Reaction of Cr+, Mn+, Fe+, Co+, and Ni+ with O2 and N2O. Examination of the translational energy dependence of the cross sections of endothermic reactions , 1982 .

[25]  E. Murad.  Abstraction reactions of Ca+ and Sr+ ions , 1983 .

[26]  J. Pedley,et al.  Thermochemical Data for Gaseous Monoxides , 1983 .

[27]  R. Lewis,et al.  A study of the first ionization potential of the CrO(X5Π) molecule with high-temperature photoelectron spectroscopy , 1983 .

[28]  P. Bagus,et al.  On the low-lying states of CuO , 1983 .

[29]  J. Bartmess,et al.  Gas-phase ion chemistry of zinc atoms and ions , 1984 .

[30]  J. Drowart,et al.  Determination of the Dissociation Energies of Gaseous Iron Monoxide and Manganese Monoxide by the Mass Spectrometric Knudsen Cell Method , 1984 .

[31]  R. Lewis,et al.  A gas phase investigation of titanium monoxide and atomic titanium using high temperature photoelectron spectroscopy , 1984 .

[32]  P. Armentrout,et al.  Translational energy dependence of Ar++XY→ArX++Y (XY=H2,D2,HD) from thermal to 30 eV c.m. , 1985 .

[33]  J. Dyke,et al.  High-temperature photoelectron spectroscopy: the vanadium monoxide molecule , 1985 .

[34]  P. B. Armentrout,et al.  Transition Metal Cluster Ion Chemistry , 1986, Photonics West - Lasers and Applications in Science and Engineering.

[35]  P. Armentrout,et al.  Effect of kinetic and electronic energy on the reactions of Cr+ with H2, HD, and D2 , 1986 .

[36]  P. Armentrout,et al.  Neutral and ionic metal methyl bond energies: zinc. , 1986, Journal of the American Chemical Society.

[37]  J. Beauchamp,et al.  Gas-phase studies of alkene oxidation by transition-metal oxides. Ion-beam studies of CrO+. , 1986, Journal of the American Chemical Society.

[38]  P. Armentrout,et al.  Effect of kinetic and electronic energy on the reactions of Fe+ with H2, HD, and D2: State-specific cross sections for Fe+(6D) and Fe+(4F) , 1986 .

[39]  M. El-Sayed.  Laser applications in chemistry and biophysics , 1986 .

[40]  P. Armentrout,et al.  Kinetic energy dependence of Al++O2→AlO++O , 1986 .

[41]  P. Armentrout,et al.  Effect of kinetic and electronic energy on the reactions of Co+, Ni+, and Cu+ with H2, HD, and D2 , 1986 .

[42]  J. F. Harrison.  The electronic and geometric structures of the chromium cations CrF+, CrO+, CrN+, and CrC+ , 1986 .

[43]  R. Levine,et al.  Molecular Reaction Dynamics and Chemical Reactivity , 1987 .

[44]  P. Armentrout,et al.  Reaction of scandium ions with ethane. First and second hydride-scandium ion bond energies , 1987 .

[45]  P. Armentrout,et al.  State-specific reactions of atomic transition-metal ions with molecular hydrogen, hydrogen deuteride, and molecular deuterium: effects of d orbitals on chemistry , 1987 .

[46]  P. Armentrout,et al.  Ammonia activation by V+: Electronic and translational energy dependence , 1987 .

[47]  P. Armentrout,et al.  Reaction of silicon ion (2P) with silane (SiH4, SiD4). Heats of formation of SiHn, SiHn+ (n = 1, 2, 3), and Si2Hn+ (n = 0, 1, 2, 3). Remarkable isotope exchange reaction involving four-hydrogen shifts , 1987 .

[48]  P. Armentrout,et al.  Energy dependence, kinetic isotope effects, and thermochemistry of the nearly thermoneutral reactions N+(3P)+H2(HD,D2)→NH+(ND+)+H(D) , 1987 .

[49]  S. Lias,et al.  Structure/Reactivity and Thermochemistry of Ions , 1987 .

[50]  P. Armentrout,et al.  Hydrogen atom transfer reactions of He+ and Ne+ with H2, D2, and HD , 1987 .

[51]  P. Armentrout,et al.  Translational energy dependence of O+(4S) + H2(D2, HD) → OH+(OD+) + H(D) from thermal energies to 30 eV c.m. , 1987 .

[52]  W. J. Stevens,et al.  Theoretical calculations of diatomic metal oxides. CrO and CrO , 1988 .

[53]  P. Armentrout,et al.  Kinetic energy dependence of the reactions of calcium(1+) and zinc(1+) with hydrogen, deuterium, and hydrogen-d1: effect of empty versus full d orbitals , 1988 .

[54]  J. Koutecký,et al.  Molecular bonding with scandium: Diatomics ScH, ScO, ScC, and ScN , 1988 .

[55]  P. Armentrout,et al.  Energetics and dynamics in the reaction of Si+ with SiF4. Thermochemistry of SiFx and SiF+x (x=1, 2, 3) , 1988 .

[56]  P. Armentrout,et al.  Periodic trends in gas phase MH and MC bond energies , 1988 .

[57]  P. Armentrout,et al.  Translational and electronic energy dependence of the reaction of Mn+ with ethane , 1989 .

[58]  P. Armentrout,et al.  State-specific reactions of iron(1+)(6D, 4F) with oxygen and oxirane: D.degree.0(iron(1+)-oxygen) and effects of collisional relaxation , 1989 .

[59]  P. Armentrout,et al.  Intrinsic transition metal-carbon double bond dissociation energies: periodic trends in M+-CH2 bond strengths , 1989 .

[60]  P. Armentrout,et al.  Thermochemistry of Ti+ hydrocarbon bonds: translational energy dependence of the reactions of Ti+ with ethane, propane, and trans-2-butene , 1989 .

[61]  P. Armentrout,et al.  Reactions of ground state Cr+ with C2H6, C2H4, cyclo-C3H6, and cyclo-C2H4O: bond energies for CrCH+n (n = 1–3) , 1989 .

[62]  P. Armentrout,et al.  The chemistry of atomic transition-metal ions: insight into fundamental aspects of organometallic chemistry , 1989 .

[63]  P. Armentrout,et al.  Ammonia activation by V+: electronic and transitional energy dependence. , 1990 .

[64]  P. Armentrout,et al.  Ammonia Activation by Sc' and Ti': Electronic and Translational Energy Dependence , 1990 .

[65]  P. Armentrout,et al.  Reactions of Mn+ with i-C4H10, neo-c5H12, (CH3)2CO, cyclo-C3H6, and cyclo-C2H4O : bond energies for MnCH2+, MnH, and MnCH3 , 1990 .

[66]  P. Armentrout,et al.  Reactions of cobalt(1+), nickel(1+), and copper(1+) with cyclopropane and ethylene oxide. Metal-methylidene ion bond energies , 1990 .