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Journal of Physical Chemistry A
Volumn 111, Issue 11, 2007, Pages 2067-2076
Influence of single impurity atoms on the structure, electronic, and magnetic properties of Ni5 clusters
Author keywords

[No Author keywords available]
Indexed keywords

CRYSTAL ATOMIC STRUCTURE; CRYSTAL IMPURITIES; DENSITY FUNCTIONAL THEORY; ISOMERS; MAGNETIC PROPERTIES; OXIDATION;
EID: 34047224336     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0675431     Document Type: Article
Times cited : (10)
References (80)
  • 14
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    • Pacchioni, G.; Krüger, S.; Rösch, N. in Ref. 13, pp 1392.
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    • Ertl, G, Knözinger, H, Weitkamp J, Eds, Wiley-VCH, Weinheim
    • Ertl, G.; Knözinger, H.; Weitkamp J. (Eds.) Handbook of Heterogeneous Catalysis Vol. 2, Wiley-VCH, Weinheim, 1997.
    • (1997) Handbook of Heterogeneous Catalysis , vol.2
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    • Belling, T, Grauschopf, T, Krüger, S, Nörtemann, F, Staufer, M, Mayer, M, Nasluzov, V. A, Birkenheuer, U, Hu, A, Matveev, A. V, Shor, A. M, Fuchs-Rohr, M. S. K, Neyman, K. M, Ganyushin, D. I, Kerdcharoen, T, Woiterski, A, Gordienko, A. B, Majumder, S, Rösch, N. PARAGAUSS, version 3.0, Technische Universität München, 2004
    • Belling, T.; Grauschopf, T.; Krüger, S.; Nörtemann, F.; Staufer, M.; Mayer, M.; Nasluzov, V. A.; Birkenheuer, U.; Hu, A.; Matveev, A. V.; Shor, A. M.; Fuchs-Rohr, M. S. K.; Neyman, K. M.; Ganyushin, D. I.; Kerdcharoen, T.; Woiterski, A.; Gordienko, A. B.; Majumder, S.; Rösch, N. PARAGAUSS, version 3.0, Technische Universität München, 2004.
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    • 1986, 34, 7406.
    • (1986) , vol.7406 , Issue.34
  • 44
    • 34047198904 scopus 로고    scopus 로고
    • Van Duijneveldt, F. B. IBM Res. Report RJ945, 1971. The basis sets have been extended by two d polarization functions for C and O, 0.5591, 19.569, and 0.3074, 1.0757, respectively, and one p function for H, 1.0000.
    • (a) Van Duijneveldt, F. B. IBM Res. Report RJ945, 1971. The basis sets have been extended by two d polarization functions for C and O, 0.5591, 19.569, and 0.3074, 1.0757, respectively, and one p function for H, 1.0000.
  • 49
    • 34047199440 scopus 로고    scopus 로고
    • The species Ni5/D3h-bp has the electronic configuration a2′1e′2e″ 1 and thus will feature a Jahn-Teller distortion of first order. The degeneracy of the HOMO is removed when the symmetry constraints are reduced to C3v in the structure Ni5/C3v-bp, which yields an electronic configuration a21e2a 11
    • 1.
  • 53
    • 34047220564 scopus 로고    scopus 로고
    • We started the optimization of Ni5+ from a square pyramid structure. During optimization the cluster distorted as the diagonals of the tetragonal base become different, 273 and 367 pm, which is to be compared to 327 pm for the diagonals of the Ni5/C4v-sp structure. The resulting structure can also be considered as distorted trigonal bipyramid where one of the equatorial Ni-Ni bonds is considerably extended to 273 pm. while the other Ni-Ni distances are 233 pm (equatorial) and 231, 236 pm axial, The deviation of the cationic cluster from both high symmetry structures can be rationalized as Jahn-Teller distortion. The HOMO, occupied by only one electron, originally is a degenerate c-type set. which splits upon distortion. The stability of the ionized species Ni5+ with respect to 4 Ni atoms and I Ni+ ion is 603 kJ/mol on average per mononuclear species
    • + ion is 603 kJ/mol on average per mononuclear species.
  • 54
    • 34047223379 scopus 로고    scopus 로고
    • The IP values were calculated also taking into account scalar relativistic effects us implemented in PARAGAUSS.52 The obtained values are: IP(vertical, 6.52 eV. IP(adiabatic, 6.29 eV for Ni 5/C3v-bp; IP(vertical, 6.81 eV, IPadiabatic, 6.63 eV for Ni5/C4v-sp. these relativistic values are by 0.05-0.17 eV higher than the non-relativistic results, and thus increase slightly the deviation from experiment compared to the non-relativistic approach
    • 4v-sp. these relativistic values are by 0.05-0.17 eV higher than the non-relativistic results, and thus increase slightly the deviation from experiment compared to the non-relativistic approach.
  • 55
    • 77956656833 scopus 로고    scopus 로고
    • Rösch, N.; Krüger, S.; Mayer, M.; Nasluzov, V. A. In Theoretical and Computational Chemistry, 4, Recent Developments and Applications of Modern Density Functional Theory: Seminario, J. Ed.; Elsevier: Amsterdam, 1996; p 497.
    • Rösch, N.; Krüger, S.; Mayer, M.; Nasluzov, V. A. In Theoretical and Computational Chemistry, Vol. 4, Recent Developments and Applications of Modern Density Functional Theory: Seminario, J. Ed.; Elsevier: Amsterdam, 1996; p 497.
  • 62
    • 34047237529 scopus 로고    scopus 로고
    • This large values of BE, obtained with the BLYP functional, is specific to the work of Xie et al, ref 56. For example, the BE per Ni atom of Ni 2, calculated with the functionals BLYP and BP. was reported to be 287 and 271 kJ/mol. respectively. These latter values are much higher than the corresponding experimental dissociation energy values of Ni2 per Ni atom, ref 61, 100 ± 1.0 kJ/mol, and the BE value calculated with the BP functional in the present work, 142 kJ/mol, ref 62
    • 2 per Ni atom, ref 61, 100 ± 1.0 kJ/mol, and the BE value calculated with the BP functional in the present work, 142 kJ/mol, ref 62.
  • 75
    • 34047216011 scopus 로고    scopus 로고
    • The overestimation of the calculated detachment energy of a Ni atom is partially due to the fact that an Oh symmetry constraint causes an overestimation of the total energy of a Ni atom. Reduction of the symmetry results in a splitting of the d-shell and removes the degeneracy. The calculation of the atomic energy is complicated because in axial symmetry the 4s and the 3dz2 AO of Ni belong to the same irreproducible representation, at, rendering it difficult to converge a configuration without holes below the HOMO. Thus, we estimated an upper limit of the atomic energy of Ni with 3d94s1 configuration in C4v and D2h symmetry where the one-electron spectra show holes, The corresponding total energies are 27 and 33 kJ/mol more stable than with Oh symmetry. Therefore, the overestimation of the experimental detachment energy for an Ni atom from the neutral Ni5 cluster is reduced from 64 kJ/mol to about
    • 5 cluster is reduced from 64 kJ/mol to about 34 kJ/mol.

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