Oxygen-Containing Diatomic Dications in the Gas Phase

Vaughan A.L. , “Mass spectrograph analyses and critical potentials for the production of ions by electron impact, in nitrogen and carbon monoxide”, Phys. Rev. 38, 1687 (1931). doi: 10.1103/PhysRev.38.1687

(a) Dorman F.H. and Morrison J.D. , “Double and triple ionization in molecules induced by electron impact”, J. Chem. Phys. 35, 575 (1961); doi: 10.1063/1.1731972 (b) Dorman F.H. and Morrison J.D. , “Erratum: Double and triple ionization in molecules induced by electron impact”, J. Chem. Phys. 36, 2808 (1962). doi: 10.1063/1.1732375

Müller E.W. Krishnaswamy S.V. and McLane S.B. , “Atom-probe FIM analysis of the interaction of the imaging gas with the surface”, Surf. Sci. 23, 112 (1970). doi: 10.1016/0039-6028(70)90008-7

Müller E.W. and Tsong T.T. , “Field ion microscopy, field ionization and field evaporation”, Progr. Surf. Sci. 4, 1 (1973). doi: 10.1016/0079-6816(73)90001-4

(a) Beynon J.H. Caprioli R.M. and Richardson J.W. , “Decomposition of metastable diatomic doubly charged positive ions”, J. Am. Chem. Soc. 93, 1852 (1971); doi: 10.1021/ja00737a003 (b) Rabrenovic M. Harris F.M. Keenan G.A. and Beynon J.H. , “The dependence of double-ionization energies of diatomic neutral species on the atomic ionization energies”, Chem. Phys. Lett. 102, 263 (1983). doi: 10.1016/0009-2614(83)87404-1

Becker S. and Dietze H.J. , “Häufigkeitsverteilungen von einfach und doppelt positiv geladenen Molekülionen ausgewählter chemischer Elemente im Funkenplasma”, Int. J. Mass Spectrom. Ion Phys. 51, 325 (1983). doi: 10.1016/0020-7381(83)85016-5

(a) Price S.D. , “Interactions of molecular doubly charged ions with atoms, molecules and photons”, J. Chem. Soc, Faraday Trans. 93, 2451 (1997); doi: 10.1039/a700808b (b) Price S.D. , “Investigating the gas-phase chemical reactions of molecular dications”, Phys. Chem. Chem. Phys. 5, 1717 (2003). doi: 10.1039/b301957h

(a) Schröder D. and Schwarz H. , “Generation, stability, and reactivity of small, multiply charged ions in the gas phase”, J. Phys. Chem. A 103, 7385 (1999); doi: 10.1021/jp991332x (b) Schröder D. Harvey J.N. and Schwarz H. , “Long-lived, multiply charged diatomic TiFⁿ⁺ ions (n = 1-3)”, J. Phys. Chem. A 102, 3639 (1998). doi: 10.1021/jp9807827

Mathur D. , “Structure and dynamics of molecules in high charge states”, Phys. Rep. 391, 1 (2004). doi: 10.1016/j.physrep.2003.10.016

Franzreb K. Hrusak J. Alikhani M.E. Lörinčík J. Sobers R.C. Jr and Williams P. , “Gas-phase diatomic trications of Se³₂⁺, Te³⁺ and LaF³⁺”, J. Chem. Phys. 121, 12293 (2004); doi: 10.1063/1.1821496 (b) Franzreb K. Hrusak J. Alikhani M.E. Lörinčík J. Sobers R.C. Jr and Williams P. , “Erratum: Gas-phase diatomic trications of Se³₂ ⁺, Te³⁺, and LaF³⁺[J. Chem. Phys. 121, 12293 (2004)]”, J. Chem. Phys. 123, 209901 (2005). doi: 10.1063/1.2135774

Pauling L. , “The normal state of the helium moleculeons He+₂ and He₂⁺⁺”, J. Chem. Phys. 1, 56 (1933). doi: 10.1063/1.1749219

(a) Bates D.R. and Carson T.R. , “Doubly charged diatomic molecular ions”, Proc. Phys. Soc. London A 68, 1199 (1955); doi: 10.1088/0370-1298/68/12/417 (b) Hurley A.C. and Maslen V.W. , “Potential curves for doubly positive diatomic ions”, J. Chem. Phys. 34, 1919 (1961); doi: 10.1063/1.1731793 (c) Hurley A.C. , “Potential energy curves for doubly positive diatomic ions, part II. Predicted states and transitions of N₂^{2 +}, O₂^{2 +}, and NO₂^2+”, J. Mol. Spectrosc. 9, 18 (1962). doi: 10.1016/0022-2852(62)90209-6

(a) Liu F. Press M.R. Khanna S.N. and Jena P. , “Stability of doubly charged transition-metal dimers”, Phys. Rev. Lett. 59, 2562 (1987); doi: 10.1103/PhysRevLett.59.2562 (b) Gill P.M.W. and Radom L. , “The ACDCP model for estimating the kinetic energy release and transition structure bond length in the fragmentation of a diatomic dication”, Chem. Phys. Lett. 147, 213 (1988); doi: 10.1016/0009-2614(88)85086-3 (c) Wong M.W. and Radom L. , “Isoelectronic analogs of phosphorus nitride: Remarkably stable multiply charged cations”, J. Phys. Chem. 94, 638 (1990). doi: 10.1021/j100365a026

(a) Ortiz G. and Ballone P. , “Metastability of doubly charged transition-metal dimers in density-functional theory”, Phys. Rev. B 44, 5881 (1991); doi: 10.1103/PhysRevB.44.5881 (b) Petrie S. , “Is the Gaussian-2 technique reliable for determining the energetics of small molecular dications?”, J. Chem. Phys. 107, 3042 (1997); doi: 10.1063/1.474660 (c) Diez Pis R. Alonso J.A. Matxain J.M. and Ugalde J.M. , “Electronic metastable bound states of Mn₂²⁺ and Co₂^2+”, Chem. Phys. Lett. 372, 82 (2003); doi: 10.1016/S0009-2614(03)00365-8 (d) Hogreve H. , “Mg₂²⁺: A long-lived metastable dication”, Chem. Phys. Lett. 394, 32 (2004); doi: 10.1016/j.cplett.2004.06.099 (e) Xie R.-H. and Gong J. , “Simple three-parameter model potential for diatomic systems: From weakly and strongly bound molecules to metastable molecular ions”, Phys. Rev. Lett. 95, 263202 (2005). doi: 10.1103/PhysRevLett.95.263202

(a) Basch H. Hoz S. and Goldberg M. , “Energy trapping in dications”, Israel J. Chem. 33, 403 (1993); (b) Kolbuszewski M. and Wright J.S. , “Thermodynamically stable diatomic dications: MgN²⁺, MgO²⁺, MgF²⁺ and MgNe²⁺”, Chem. Phys. Lett. 218, 338 (1994); doi: 10.1016/0009-2614(94)E1489-H (c) Schröder D. Engeser M. Schwarz H. and Harvey J.N. , “Energetics of the ligated vanadium dications VO²⁺, VOH²⁺, and [V,O,H₂]^2+”, Chem. Phys. Chem. 3, 584 (2002).

A SIMS experiment very similar to ours, and with the same type of SIMS instrument as used in the present study, had previously been made by Holland and Blackmore to observe the novel diatomic dications CdO²⁺ and TeO²⁺.¹⁷ High-current ¹⁶O₂⁺ oxygen ion surface bombardment had been applied in Reference 17, whereas ¹⁶O⁻ ion beam sputtering was used in the present work. Recently we have also observed CdO²⁺ and TeO²⁺ by means of ¹⁶O⁻ sputtering (unpublished results).

Holland R. and Blackmore G.W. , “The quantitative application of SIMS to cadmium mercury telluride”, Int. J. Mass Spectrom. Ion Phys. 46, 527 (1983). doi: 10.1016/0020-7381(83)80168-5

Franzreb K. and Williams P. , unpublished experimental results. [Please contact Klaus Franzreb (e-mail: klaus.franzreb@asu.edu) for further information. With respect to negative results, we could not observe BO²⁺, PdO²⁺, CsO²⁺ and HgO²⁺.]

(a) Liu X.D. Verlinden J. Adams F. and Adriaenssens E. , “Analysis of high purity arsenic by Spark-Source Mass Spectrometry”, Anal. Chim. Acta 180, 341 (1986); doi: 10.1016/0003-2670(86)80016-2 (b) Verlinden J. Gijbels R. and Adams F. , “Applications of spark-source mass spectrometry in the analysis of semiconductor-materials—a review”, J. Anal. Atomic Spectrom. 1, 411 (1986). doi: 10.1039/ja9860100411

Grovenor C.R.M. and Cerezo A. , “Atom probe studies of the composition of low-temperature oxides on (100) silicon and gallium arsenide surfaces”, J. Appl. Phys. 65, 5089 (1989). doi: 10.1063/1.343185

The assignment to GaO²⁺ (label in Figure 3 in Reference 22) does not appear to be supported by the Atom Probe data shown in Reference 22.

Ohno Y. Kuroda T. and Nakamura S. , “Atom-probe field-ion microscopy of GaAs and GaP”, Surf. Sci. 75, 689 (1978). doi: 10.1016/0039-6028(78)90186-3

Kellogg G.L. , “Field ion microscopy and pulsed laser atom-probe mass spectroscopy of insulating glasses”, J. Appl. Phys. 53, 6383 (1982); (b) Melmed A.J. and Camus P.P. , “Composite thin-film characterization by atom probe field ion microscopy”, Ultramicroscopy 35, 277 (1991). doi: 10.1016/0304-3991(91)90080-P

(a) Yoshimura T. Koguchi Y. , and Ishikawa Y. , “An atom-probe study of passivated surface of a stainless steel”, Journal de Physique (Colloque) 48, C6–417 (1987); doi: 10.1051/jphyscol:1987668 (b) Ren D.G. , “Study of interface structure of the oxide grown on nickel alloys by AP-FIM”, Appl. Surf. Sci. 48/49, 227 (1991); doi: 10.1016/0169-4332(91)90335-H (c) Ohkido S. Ishikawa Y. and Yoshimura T. , “POSAP analysis of the oxide-alloy interface in stainless steel”, Appl. Surf. Sci. 76/77, 261 (1994); doi: 10.1016/0169-4332(94)90352-2 (d) Yoshimura T. Ishikawa Y. and Ohkido S. , “Analysis of oxide film on stainless steel via position-sensitive atom probe”, J. Vac. Sci. Technol. A 12, 2544 (1994). doi: 10.1116/1.579054

(a) Galindo-Uribarri A. Lee H.W. and Chang K.H. , “Beams of doubly ionized molecules from a tandem accelerator”, J. Chem. Phys. 83, 3685 (1985); doi: 10.1063/1.449123 (b) Zhao X.-L. Nadeau M.-J. Garwan M.A. Kilius L.R. , and Litherland A.E. , “A new method for the separation of the isobars ⁷Be−⁷Li”, Nucl. Instrum. Meth. Phys. Res. B 52, 416 (1990). doi: 10.1016/0168-583X(90)90448-4

(a) Harvey J.N. Heinemann C. Fiedler A. Schröder D. and Schwarz H. , “Redox properties of the diatomic bare iron chalcogenides FeO and FeS in the gas phase”, Chem. Eur. J. 2, 1230 (1996); doi: 10.1002/chem.19960021008 (b) Schröder D. Schwarz H. and Harvey J.N. , “LaO⁺: A diatomic cation with a sizable proton affinity upon generation of the LaOH²⁺ dication”, J. Phys. Chem. A 104, 11257 (2000); doi: 10.1021/jp002892v (c) J. Fišer and R. Polák, Chem. Phys. Lett., submitted.

17 keV ¹⁶O⁻ sputtering with a similar SIMS instrument was previously applied by Riciputi et al.²⁸ for quantitative trace analysis of rare earth elements (REE) X in silicates, that were monitored as mono-atomic dication signals X²⁺ at half-integer m/z values. Riciputi et al. reported that doubly-charged oxide ions XO²⁺ (with observed signal ratios of XO²⁺: X²⁺ of roughly 10⁻⁴) of light REE elements could cause mass interferences at half-integer m/z values with atomic dication signals of heavier REE elements, for example, Gd.²⁸ (This example includes the mass interferences of ¹³⁹La¹⁶O^{2+ 6} with ¹⁵⁵Gd²⁺ and of 141Pr16O2+ 6 with 157Gd2+.).

Riciputi L.R. Christie W.H. Cole D.R. and Rosseel T.M. , “Analysis for rare earth elements in silicates by ion microprobe using doubly-charged ions”, Anal. Chem. 65, 1186 (1993). doi: 10.1021/ac00057a014

For detection of ⁹Be¹⁶O²⁺ at sufficiently high mass resolution to achieve mass separation from ²⁵Mg²⁺ (see right-side inset of Figure 5), the entrance and exit slits of the secondary magnet of our mass spectrometer were partially closed. This caused a reduction of the ion signals by about a factor of ∼10. (Note that in Figure 5 the ¹⁶O⁻ primary ion density was increased for BeO²⁺ detection at high mass resolution.).

Werner H.-J. and Knowles P.J. , “An efficient internally contracted multiconfiguration–reference configuration interaction method”, J. Chem. Phys. 89, 5803 (1988). doi: 10.1063/1.455556

Knowles P.J. and Werner H.-J. , “An efficient method for the evaluation of coupling coefficients in configuration interaction calculations”, Chem. Phys. Lett. 145, 514 (1988). doi: 10.1016/0009-2614(88)87412-8

Gdanitz R.J. and Ahlrichs R. , “The averaged coupled-pair functional (ACPF): A size-extensive modification of MR CI(SD)”, Chem. Phys. Lett. 143, 413 (1988). doi: 10.1016/0009-2614(88)87388-3

Raghavachari K. Trucks G.W. Pople J.A. and Head-Gordon M. , “A fifth-order perturbation comparison of electron correlation theories”, Chem. Phys. Lett. 157, 479 (1989). doi: 10.1016/S0009-2614(89)87395-6

Knowles P. Hampel C. and Werner H.-J. , “Coupled cluster theory for high spin, open shell reference wave functions”, J. Chem. Phys. 99, 5219 (1993). doi: 10.1063/1.465990

MOLPRO 2006.1 is a package of ab initio programs written by Werner H.-J. and Knowles P.J. , with contributions from Amos R.D. Bernhardsson A. Berning A. Celani P. Cooper D.L. Deegan M.J.O. Dobbyn A.J. Eckert F. Hampel C. Hetzer G. Korona T. Lindh R. Lloyd A.W. McNicholas S.J. Manby F.R. Meyer W. Mura M.E. Nicklass A. Palmieri P. Pitzer R. Rauhut G. Schütz M. Stoll H. Stone A.J. Tarroni R. and Thorsteinsson T. ; see http://www/molpro.net .

Langhoff S.R. and Davidson E.R. , “Configuration interaction calculations of the nitrogen molecule”, Int. J. Quantum Chem. 8, 61 (1974). doi: 10.1002/qua.560080106

Dunning T.H. Jr , “Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen”, J. Chem. Phys. 90, 1007 (1989). doi: 10.1063/1.456153

Halkier A. Helgaker T. Jørgensen P. Klopper W. Koch H. Olsen J. and Wilson A.K. , “Basis-set convergence in correlated calculations on Ne, N₂, and H₂O”, Chem. Phys. Lett. 286, 243 (1998). doi: 10.1016/S0009-2614(98)00111-0

Helgaker T. Klopper W. Koch H. and Noga J. , “Basis-set convergence of correlated calculations on water”, J. Chem. Phys. 106, 9639 (1997). doi: 10.1063/1.473863

MOLCAS-4 is a package of ab initio programs written by Andersson K. Blomberg M.R.A. Fülscher M.P. Karlström G. Lindh R. Malmqvist P.-Å. Neogrády P. Olsen J. Roos B.O. Sadlej A.J. Schütz M. Seijo L. Serrano-Andrés L. Siegbahn P.E.M. and Widmark P.-O. , Lund University, Sweden, (1997).

LeRoy R.J. , LEVEL8.1 program; see http://scienide.uwaterloo.ca/∼leroy/level.

Our observation of the diatomic dications AsO²⁺ and GaO²⁺ had been briefly mentioned previously (data not shown) in Table II in Reference 10.

Schauer S.N. and Williams P. , “Doubly charged sputtered ions of fourth-row elements”, Phys. Rev. B 46, 15452 (1992). doi: 10.1103/PhysRevB.46.15452

Kolbuszewski M. and Wright J.S. , “Predicting thermodynamic stability of diatomic dications—a case study of BeF²⁺”, Can. J. Chem. Rev. Can. Chim. 71, 1562 (1993). doi: 10.1139/v93-196

Lee E.P.F. Soldán P. and Wright T.G. , “High-level ab initio study of LiO (X²Π;A²Σ⁺) and LiO⁺ (X³Σ⁻;A³Π): The ionization energy of LiO”, Chem. Phys. Lett. 347, 481 (2001). doi: 10.1016/S0009-2614(01)01069-7

Boldyrev A.I. Simons J. and Schleyer P.V.R. , “Ab initio study of the electronic structures of lithium containing diatomic molecules and ions”, J. Chem. Phys. 99, 8793 (1993). doi: 10.1063/1.465600

Teberekidis V.I. Kerkines I.S.K. Tsipis C.A. Čársky P. and Mavridis A. , “Ground states of BeC and MgC: A comparative multireference Brillouin–Wigner coupled cluster and configuration interaction study”, Int. J. Quantum Chem. 102, 762 (2005). doi: 10.1002/qua.20379

Ascenzi D. Franceschi P. Tosi P. Bassi D. Kaczorowska M. and Harvey J.N. , “Bond-forming reactions of dications: Production of ArO⁺ and ArO²⁺ in the reaction of Ar²⁺ with O₂”, J. Chem. Phys. 118, 2159 (2003). doi: 10.1063/1.1533751

Douglas M. and Kroll N.M. , “Quantum electrodynamical corrections to fine-structure of helium”, Ann. Phys. (N.Y.) 82, 89 (1974). doi: 10.1016/0003-4916(74)90333-9

Jansen G. and Hess B.A. , “Revision of the Douglas–Kroll transformation”, Phys. Rev. A 39, 6016 (1989). doi: 10.1103/PhysRevA.39.6016

Huber K.P. and Herzberg G. , Molecular spectra and molecular structure IV. Constants of diatomic molecules. Van Nostrand, New York, USA (1979).

Nakamura S. Ng Y.S. Tsong T.T. and McLane S.B. Jr , “ToF atom-probe FIM study of LaB₆ single crystals”, Surf. Sci. 87, 656 (1979). doi: 10.1016/0039-6028(79)90557-0

Ghalila H. Lahmar S. Ben Lakhdar Z. and Hochlaf M. “Spectroscopy and metastability of BeO⁺”, J. Phys. B: At. Mol. Opt. Phys. 41, 205101 (2008). doi: 1088/0953-4075/41/20/205101