Theoretical Chemistry Accounts

, 135:258 | Cite as

Study on the structures and properties of praseodymium-doped silicon clusters PrSi n (n = 3–9) and their anions with density functional schemes

Regular Article
First Online:
Received:
Accepted:

Abstract

The equilibrium geometries and properties such as adiabatic electron affinities (AEAs), simulated photoelectron spectra (PES), dissociation energies, relative stabilities, HOMO–LUMO gaps, charges transfer, and magnetic moments of PrSi n (n = 3–9) and their anions have been made a detailed study by means of the ABCluster global search technique combined with density functional methods. The structure optimization is carried out with three exchange correlation functionals (B3LYP, PBE0, and mPW2PLYP). The ground state structures predicted by mPW2PLYP are thought to be trustworthy. The experimental PES of PrSi4 − is reassigned in light of the theoretical results, and the experimental AEAs of 2.0 ± 0.1 eV are obtained. The mPW2PLYP AEAs of PrSi n are in excellent agreement with the experimental values. The average absolute deviations from experiment are only 0.05 eV, and the maximum deviations are 0.10 eV. The accordance between the experimental PES and the theoretical simulations indicates that the ground state structures of PrSi n − (n = 4–9) are trustworthy. Doping Pr atom to Si n (n = 3–9) clusters raises the photochemical sensitivity. A large proportion of the total magnetic moments for all of these species are contributed by Pr atom.

Keywords

PrSin Ground state structures Electron affinities Charge transfer Magnetic moment 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgements

We thank Prof. Kit H. Bowen for providing the clear experimental PES of PrSi n (n = 4–9). This work was supported by the National Natural Science Foundation of China (Grant No. 21263010), by Program for Innovative Research Team in Universities of Inner Mongolia Autonomous Region (Gran No. NMGIRT-A1603), and by the Inner Mongolia Natural Science Foundation (Grant No. 2015MS0216).

References

  1. 1.
    Grubisic A, Ko YJ, Wang HP, Bowen KH (2009) Photoelectron spectroscopy of lanthanide–silicon cluster anions LnSin− (3 ≤ n ≤ 13; Ln = Ho, Gd, Pr, Sm, Eu, Yb): prospect for magnetic silicon-based clusters. J Am Chem Soc 131:10783–10790CrossRefGoogle Scholar
  2. 2.
    Grubisic A, Wang HP, Ko YJ, Bowen KH (2008) Photoelectron spectroscopy of europium-silicon clusters anions, EuSin− (3 ≤ n ≤ 17). J Chem Phys 129:054302-1–054302-5CrossRefGoogle Scholar
  3. 3.
    Ohara M, Miyajima K, Pramann A, Nakajima A, Kaya K (2002) Geometric and electronic structures of terbium–silicon mixed clusters (TbSin; 6 ≤ n ≤ 16). J Phys Chem A 106:3702–3705CrossRefGoogle Scholar
  4. 4.
    Koyasu K, Atobe J, Furuse S, Nakajima A (2008) Anion photoelectron spectroscopy of transition metal- and lanthanide metal-silicon clusters: MSin− (n = 6–20). J Chem Phys 129:214301-3–214301-7CrossRefGoogle Scholar
  5. 5.
    Kenyon AJ (2005) Erbium in silicon. Semicond Sci Technol 20:R65–R84CrossRefGoogle Scholar
  6. 6.
    Zhao RN, Han JG (2014) Geometrical stabilities and electronic properties of Sin (n = 12–20) clusters with rare earth holmium impurity: a density functional investigation. RSC Adv 4:64410–64418CrossRefGoogle Scholar
  7. 7.
    Zhao GF, Sun JM, Gu YZ, Wang YX (2009) Density-functional study of structural, electronic, and magnetic properties of the EuSin (n = 1–13) clusters. J Chem Phys 131:114312-1–114312-7Google Scholar
  8. 8.
    Xu W, Ji WX, Xiao Y, Wang SG (2015) Stable structures of LnSi6 − and LnSi6 (Ln = Pr, Eu, Gd, Tb, Yb), C2v or C5v? Explanation of photoelectron spectra. Comput Theor Chem 1070:1–8CrossRefGoogle Scholar
  9. 9.
    Li CG, Pan LJ, Shao P, Ding LP, Feng HT, Luo DB, Liu B (2015) Structures, stabilities, and electronic properties of the neutral and anionic SinSmλ (n = 1–9, λ = 0, −1) clusters: comparison with pure silicon clusters. Theor Chem Acc 134:34-1-11Google Scholar
  10. 10.
    Zhao RN, Ren ZY, Guo P, Bai JT, Zhang CH, Han JG (2006) Geometries and electronic properties of the neutral and charged rare earth Yb-doped Sin (n = 1–6) clusters: a relativistic density functional investigation. J Phys Chem A 110:4071–4079CrossRefGoogle Scholar
  11. 11.
    Zhao RN, Han JG, Bai JT, Liu FY, Sheng LS (2010) A relativistic density functional study of Sin (n = 7–13) clusters with rare earth ytterbium impurity. Chem Phys 372:89–95CrossRefGoogle Scholar
  12. 12.
    Zhao RN, Han JG, Bai JT, Liu FY, Sheng LS (2010) The medium-sized charged YbSin± (n = 7–13) clusters: a relativistic computational investigation. Chem Phys 378:82–87CrossRefGoogle Scholar
  13. 13.
    Cao TT, Zhao LX, Feng XJ, Lei YM, Luo YH (2009) Structural and electronic properties of LuSin (n = 1–12) clusters: a density functional theory investigation. J Mol Struct TheoChem 895:148–155CrossRefGoogle Scholar
  14. 14.
    Liu TG, Zhang WQ, Li YL (2014) First-principles study on the structure, electronic and magnetic properties of HoSin (n = 1–12, 20) clusters. Front Phys 9:210–218CrossRefGoogle Scholar
  15. 15.
    Cao TT, Feng XJ, Zhao LX, Liang X, Lei YM, Luo YH (2008) Structure and magnetic properties of La-doped Sin (n = 1–12, 24) clusters: a density functional theory investigation. Eur Phys J D 49:343–351CrossRefGoogle Scholar
  16. 16.
    Peng Q, Shen J (2008) Growth behavior of La@Sin (n = 1–21) metal-encapsulated clusters. J Chem Phys 128:084711-1-11CrossRefGoogle Scholar
  17. 17.
    Liu TG, Zhao GF, Wang YX (2011) Structural, electronic and magnetic properties of GdSin (n = 1–17) clusters: a density functional study. Phys Lett A 375:1120–1127CrossRefGoogle Scholar
  18. 18.
    Xie XH, Hao DS, Yang JC (2015) Ytterbium doped silicon clusters YbSin (n = 4–10) and their anions: structures, thermochemistry, and electron affinities. Chem Phys 461:11–19CrossRefGoogle Scholar
  19. 19.
    Xie XH, Hao DS, Liu YM, Yang JC (2015) Samarium doped silicon clusters SmSin (n = 3–10) and their anions: structures, thermochemistry, electron affinities, and magnetic moments. Comput Theor Chem 1074:1–8CrossRefGoogle Scholar
  20. 20.
    Yang JC, Wang J, Hao YR (2015) Europium-doped silicon clusters EuSin (n = 3–11) and their anions: structures, thermochemistry, electron affinities, and magnetic moments. Theor Chem Acc 134:81-1-11Google Scholar
  21. 21.
    Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652CrossRefGoogle Scholar
  22. 22.
    Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789CrossRefGoogle Scholar
  23. 23.
    Adamo C, Barone V (1999) Toward reliable density functional methods without adjustable parameters: the PBE0 model. J Chem Phys 110:6158–6170CrossRefGoogle Scholar
  24. 24.
    Schwabe T, Grimme S (2006) Towards chemical accuracy for the thermodynamics of large molecules: new hybrid density functionals including non-local correlation effects. Phys Chem Chem Phys 8:4398–4401CrossRefGoogle Scholar
  25. 25.
    Woon DE, Dunning TH Jr (1993) Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon. J Chem Phys 98:1358–1371CrossRefGoogle Scholar
  26. 26.
    Cao X, Dolg M (2002) Segmented contraction scheme for small-core lanthanide pseudopotential basis sets. J Mol Struct Theochem 581:139–147CrossRefGoogle Scholar
  27. 27.
    Buchachenko AA, Chalasiński G, Szcześniak MM (2007) Diffuse basis functions for small-core relativistic pseudopotential basis sets and static dipole polarizabilities of selected lanthanides La, Sm, Eu, Tm and Yb. Struct Chem 18:769–772CrossRefGoogle Scholar
  28. 28.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V et al (2010) Gaussian 09 revision C.01. Gaussian Inc., WallingfordGoogle Scholar
  29. 29.
    Zhang J, Dolg M (2015) ABCluster: the artificial bee colony algorithm for cluster global optimization. Phys Chem Chem Phys 17:24173–24181CrossRefGoogle Scholar
  30. 30.
    Dolg M, Stoll H, Savin A, Preuss H (1989) Energy-adjusted pseudopotentials for the rare earth elements. Theor Chim Acta 75:173–194CrossRefGoogle Scholar
  31. 31.
    Dolg M, Stoll H, Preuss H (1993) A combination of quasirelativistic pseudopotential and ligand field calculations for lanthanoid compounds. Theor Chim Acta 85:441–450CrossRefGoogle Scholar
  32. 32.
    Yang JC, Xu WG, Xiao WS (2005) The small silicon clusters Sin (n = 2–10) and their anions: structures, themochemistry, and electron affinities. J Mol Struct Theochem 719:89–102CrossRefGoogle Scholar
  33. 33.
    Sekiya M, Noro T, Koga T, Shimazaki T (2012) Relativistic segmented contraction basis sets with core-valence correlation effects for atoms 57La through 71Lu: Sapporo-DK-nZP sets (n = D, T, Q). Theor Chem Acc 131:124-7-18CrossRefGoogle Scholar
  34. 34.
    Noro T, Sekiya M, Koga T (2012) Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q). Theor Chem Acc 131:112-4-18CrossRefGoogle Scholar
  35. 35.
    Tozer DJ, Handy NC (1998) Improving virtual Kohn-Sham orbitals and eigenvalues: application to excitation energies and static polarizabilities. J Chem Phys 109:10180–10189CrossRefGoogle Scholar
  36. 36.
    Sporea C, Rabilloud F, Cosson X, Allouche AR, Frécon M (2006) Theoretical study of mixed silicon-lithium clusters SinLip(+) (n = 1–6, p = 1–2). J Phys Chem A 110:6032–6038CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.School of Energy and Power EngineeringInner Mongolia University of Technology, and Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry SimulationHohhotPeople’s Republic of China
  2. 2.School of Chemical EngineeringInner Mongolia University of TechnologyHohhotPeople’s Republic of China

Personalised recommendations