No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The electronic structure of small nickel atom clusters
1.(a) R. C. Baetzold and R. E. Mack, J. Chem. Phys. 62, 1513 (1975);
1.(b) R. C. Baetzold, Adv. Catal. 25, 1 (1976).
2.D. J. M. Fassaert, H. Verbeck, and A. van der Avoird, Surf. Sci. 29, 501 (1972).
3.L. W. Anders, R. S. Hansen, and L. S. Bartell, J. Chem. Phys. 59, 5277 (1973);
3.L. W. Anders, R. S. Hansen, and L. S. Bartell, 62, 1641 (1975)., J. Chem. Phys.
4.(a) A. B. Anderson and R. Hoffman, J. Chem. Phys. 63, 4545 (1974);
4.(b) A. B. Anderson, J. Chem. Phys. 64, 4046 (1976);
4.(c) A. B. Anderson, J. Chem. Phys. 66, 5108 (1977).
5.G. Blyholder, J. Chem. Phys. 62, 3193 (1975);
5.G. Blyholder, Surf. Sci. 42, 249 (1974).
6.N. Rosch and D. Menzel, Chem. Phys. 13, 243 (1976).
7.(a) R. P. Messmer, C. W. Tucker, Jr., and K. H. Johnson, Chem. Phys. Lett. 36, 423 (1975);
7.(b) R. P. Messmer, S. K. Knudson, K. H. Johnson, J. B. Diamond, and C. Y. Yang, Phys. Rev. B 13, 1396 (1976);
7.(c) R. P. Messmer, D. R. Salahub, H. H. Johnson, and C. N. Yang, Chem. Phys. Lett. 51, 84 (1977);
7.(d) R. P. Messmer, Modern Theoretical Chemistry, Vol. 8, edited by G. A. Segal (Plenum, New York, 1977), p. 215.
8.(a) J. W. Lauher, J. Am. Chem. Soc. 100, 5305 (1978);
8.(b) J. W. Lauher, J. Am. Chem. Soc. 101, 2604 (1979).
9.R. J. Madix, J. Vac. Sci. Technol. 13, 253 (1976).
10.(a) M. Moskovitz and G. A. Ozin, J. Chem. Phys. 58, 1251 (1973);
10.(b) E. P. Kundig, D. McIntoch, M. Moskovitz, and G. A. Ozin, J. Am. Chem. Soc. 95, 7234 (1973);
10.(c) G. A. Ozin and W. J. Power, Inorg. Chem. 16, 212 (1977).
11.(a) K. G. Caulton, M. G. Thomas, B. A. Sosinsky, and E. L. Muetterties, Proc. Natl. Acad. Sci. (USA) 73, 4274 (1976);
11.(b) E. L. Muetterties, T. N. Rhodin, E. Band, C. F. Brucker and W. R. Pretzer, Chem. Rev. 79, 91 (1979).
12.H. Conrad, G. Ertl, H. Knozinger, J. Kuppers, and E. E. Latta, Chem. Phys. Lett. 42, 115 (1976).
13.J. W. Lannett, D. L. Perry, and W. F. Egelhoff, Chem. Phys. Lett. 36, 331 (1975).
14.G. C. Bond, in Electronic Structure and Reactivity of Metal Surfaces, edited by E. G. Derouane and A. A. Lucas (Plenum, New York, 1976), p. 523.
15.G. A. Ozin, Acc. Chem. Res. 10, 21 (1977);
15.W. Koltzbucker and G. A. Ozin, Inorg. Chem. 16, 984 (1977).
16.M. Moskovitz and J. E. Hulse, J. Chem. Phys. 66, 3988 (1977).
17.(a) C. F. Melius, J. W. Moskowitz, A. P. Mortola, M. G. Baile, and M. A. Ratner, Surf. Sci. 59, 279 (1976);
17.(b) C. F. Melius, Chem. Phys. Lett. 39, 287 (1976).
18.T. H. Upton and W. A. Goddard III, J. Am. Chem. Soc. 100, 5659 (1978).
19.J. O. Noell, M. D. Newton, P. J. Hay, R. L. Martin, and F. W. Bobrowicz, J. Chem. Phys. 73, 2360 (1980).
20.C. F. Melius, B. D. Olafson, and W. A. Goddard III, Chem. Phys. Lett. 28, 457 (1974).
21.I. Shim, J. P. Dahl, and H. Joahnson, Int. J. Quantum Chem. XV, 311 (1979).
22.J. Harris and R. D. Jones, J. Chem. Phys. 70, 830 (1979).
23.J. C. Slater, J. B. Mann, T. M. Wilson, and J. H. Wood, Phys. Rev. 184, 672 (1969).
24.J. C. Slater and K. H. Johnson, Phys. Rev. B 5, 844 (1972).
25.K. H. Johnson, J. G. Norman, and J. W. D. Connoly, in Computational Methods for Large Molecules and Localized States in Solids, edited by F. Herman, A. D. McLean and R. K. Nesbet (Plenum, New York, 1973), p. 161.
26.J. W. D. Connolly, Modern Theoretical Chemistry, Vol. 7, edited by G. A. Segal (Plenum, New York, 1977), p. 105.
27.While Ref. 22 reported a ground state, it should be noted that the lowest state in he LSD model arises from a hole state [J. D. Harris (private communication)], in contrast to the ab initio calculations of Refs. 18, 19, and 21, which found the configuration to give a lower state.
28.N. Rosch and T. N. Rhodin, Phys. Rev. Lett. 32, 1189 (1974);
28.N. Rosch and T. N. Rhodin, Faraday Discuss. Chem. Soc. 58, 28 (1974).
29.R. J. Smith, J. Anderson, H. Hermanson, and G. J. Lapeyre, Solid State Commun. 21, 459 (1977).
30.J. H. Wood, Chem. Phys. Lett. 51, 582 (1977).
31.(a) B. Moraweck, G. Clugnet, and A. J. Renouprez, Surf. Sci. 81, 631 (1979);
31.(b) G. Apai, J. F. Hamilton, J. Stohr, and A. Thompson, Phys. Rev. Lett. 43, 165 (1979);
31.(c) G. H. Via, J. H. Sinfelt, and F. W. Lytle, J. Chem. Phys. 71, 690 (1979).
32.C. D. Gelatt, H. Ehrenreich, and R. E. Watson, Phys. Rev. B 15, 1613 (1977).
33.P. J. Hay, J. Chem. Phys. 66, 4377 (1977).
34.J. Harris and R. O. Jones, J. Chem. Phys. 68, 3316 (1978).
35.(a) T. H. Upton, W. A. Goddard III, and C. F. Melius, J. Vac. Sci. Technol. 16, 531 (1979);
35.(b) S. P. Walch and W. A. Goddard III, Surf. Sci. 72, 645 (1978).
36.C. Kittel, Elementary Solid State Physics (Wiley, New York, 1962).
37.L. R. Kahn, P. Raybutt, and D. G. Truhlar, J. Chem. Phys. 65, 3826 (1976).
38.S. Topiol, J. W. Moskowitz, and C. F. Melius, J. Chem. Phys. 68, 2364 (1978).
39.C. Froese‐Fischer, Comput. Phys. Commun. 4, 107 (1972).
40.C. E. Moore, Atomic Energy Levels, Natl. Bur. Stand. Circ. 467 (1952).
41.A. J. H. Wachters, J. Chem. Phys. 52, 1033 (1970).
42.S. P. Walch and W. A. Goddard III, J. Am. Chem. Soc. 98, 7908 (1976).
43.C. F. Melius, C. L. Brisson, and W. D. Wilson, Phys. Rev. B 18, 1647 (1978).
44.B. Roos, A. Veillard, and G. Vinot, Theor. Chim. Acta 1, 20 (1971).
45.All six linearly independent second order Cartesian GTOs were used ( ) on each center. The ‐type basis function included in this set was found to be of only minor importance for the electronic structure (e.g., its contribution to the valence orbital population was small and essentially constant for all the different clusters, ranging between and ), and no further mention will be made of it.
46.For example, see J. P. Daudey, J. P. Malrieu, and O. Rojas, Int. J. Quantum Chem. 8, 17 (1974).
47.W. J. Hunt, W. A. Goddard III, and T. H. Dunning, Jr., J. Chem. Phys. Lett. 6, 147 (1970).
48.I.e., relative to the unrelaxed I. P. for the majority spin multiplet, the I. P. multiplied by is increased by where K is the exchange integral between orbitals and and the sum is over all singly occupied orbitals m.
49.A. Kant, J. Chem. Phys. 41, 1872 (1964).
50.W. F. Cooper, G. A. Clarke, and C. R. Hare, J. Phys. Chem. 76, 2268 (1972).
51.The ODC wave function at infinite separation causes some to mix with the predominant state of each atom.
52.Based on a two‐configuration wave function of the form with MOs taken from the ground state ODC wave function. Larger CI calculations indicate little mixing between the states arising from the and states of the atoms.
53.Even for the cases cited in Table VII exact localization will not in general be obtained, as can be seen for example by considering the hole state of One expects, and indeed finds, that the holes involve primarily some mixture of the and AOs, both of which fully span the set. However, to the extent that mixes into the holes, perfect localization will not be possible because a corresponding mixing of into the MO is not possible.
54.(a) For example, the nickel orbital is found mainly in the and molecular orbitals of the MCSCF wave function. Analogously, and and and Note that the AO character of the MCSCF orbitals is different from that of open‐shell single configuration SCF orbitals (e.g., in the latter case, the set is primarily ).
54.(b) The closed‐shell SCF ground state is related to configuration (8) by the transfer
55.An energy higher by 0.1 eV was obtained for an alternative model, in which the localized hole on each basal Ni atom is antisymmetric with respect to a plane containing the relevant atomic center and the fourfold symmetry axis [cf. Ref. 35(b)].
56.J. S. Griffith, J. Inorg. Nucl. Chem. 3, 15 (1956).
57.See Ref. 8(a) and references cited therein.
58.The state can be represented as a single determinant of the form where all other spin orbitals are fully occupied, and the pair refers to real Cartesian orbitals of the type or a, b, c denote the Cartesian axes. A pair of MOs is defined here to have a sigma‐delta relationship if their respective constituent AOs on a given center are of the above type.
59.(a) Several cluster complexes involving a tetrahedron or distorted tetrahedron have been studied structurally. The undistorted clusters have yielded Ni‐Ni distances of 2.51 Å [M. J. Burnett and B. H. C. Winquest, J. Am. Chem. Soc. 89, 5366 (1967)],
59.and 2.47 Å [T. F. Koetzle, J. Muller, D. L. Tipton, D. W. Hart, and R. Bau, J. Am. Chem. Soc. 101, 563 (1979)],
59.values which are close to the bulk value, although part of the lengthening (relative to ) may be the consequence of bonding to the peripheral ligands which will occur at the expense of cluster metal‐metal bonding. The two examples of trigonally distorted tetrahedra [V. W. Day, R. O. Day, J. S. Kristoff, F. J. Hirsekom, and E. L. Muetterties, J. Am. Chem. Soc. 97, 2572 (1975),
59.and M. G. Thomas, E. L. Muetterties, R. O. Day, and V. W. Day, J. Am. Chem. Soc. 98, 4645 (1976)] yield apical‐basal Ni‐Ni distances of 2.34–2.37 Å.
59.(b) See also the general discussion by P. Chini and B. T. Heaton, Topics Current Chem. 71, 1 (1977).
60.(a) H. Basch, M. D. Newton, and J. W. Moskowitz, J. Chem. Phys. 69, 584 (1978);
60.(b) G. A. Ozin, W. J. Power, T. H. Upton, and W. A. Goddard III, J. Am. Chem. Soc. 100, 4750 (1978).
61.J. A. Connor, Topics Current Chem. 71, 71 (1977).
62.The constrained calculations are of limited significance because there is no unique way to orthogonalize the various non‐orthogonal s, p and d‐type MOs when the constraints are imposed. The procedure of simply Schmidt orthogonalizing the s,p set to the d set (when only sp hybridization was being allowed) or orthogonalizing the pd set to the s set (for pd hybridization only) appeared to yield the lowest total energies.
63.J. Callaway and C. S. Wing, Phys. Rev. B 7, 1096 (1973).
64.R. P. Messmer, D. R. Salahub, K. H. Johnson, and C. Y. Yang, Chem. Phys. Lett. 51, 84 (1977).
65.(a) It is interesting to note that the DOS diagram for the cluster in Fig. 5(a) bears a striking resemblence to the ultraviolet photoemission spectrum of bulk copper65b;
65.(b) J. Stohr, P. S. Wehner, R. S. Williams, G. Apai, and D. A. Shirley, Phys. Rev. B 17, 587 (1978).
66.Blyholdera5 noted in his CNDO calculations on nickel atom clusters that for linear and planar species the lowest orbital is of d type but for three‐dimensional clusters that lowest orbital is of primarily character. Figure 2 shows, however, that these trends are not obtained in the ab initio results.
67.(a) M. G. Mason, L. J. Gerensen, and S. T. Lee, Phys. Rev. Lett. 39, 288 (1977);
67.(b) R. C. Baetzold, M. G. Mason, and J. F. Hamilton, J. Chem. Phys. 72, 366 (1980).
Article metrics loading...
Full text loading...
Most read this month
Most cited this month