Open Access Open Access  Restricted Access Subscription Access

A computational study on structure and stability of nitrogen-doped titanium clusters TinN (n = 1-10)

Le Nguyen Ngoc Lan, Huynh Thanh Nam, Chau Hung Cuong, Nguyen Tien Trung, Vu Thi Ngan


A study was performed using density functional theory at the PW91PW91/DGDZVP2 level to investigate the structures and stability of the neutral nitrogen-doped titanium clusters TinN (n = 1-10). The most stable isomers may have spin state ranging from doublet to quartet to sextet. Interestingly, the ground-state structures of these clusters are consistently formed by adding an N atom on an edge and a face of the pure titanium cluster and the N atom prefers to stay on surface of the clusters. Doping with an N atom increases the stability of titanium clusters and decreases their metallicity. Moreover, the analyses of average binding energy, second-order energy differences and fragmentation energy according to cluster size imply a special stability of Ti6N.

Keywords. N-doped titanium clusters, PW91PW91 functional, cluster stability, electronic structure, HOMO‑LUMO gap.


N-doped titanium clusters, PW91PW91 functional, cluster stability, electronic structure, HOMO‑LUMO gap

Full Text:



J. A. Alonso. Electronic and atomic structure, and magnetism of transition-metal clusters, Chem. Rev., 100, 637 (2000).

R. Ferrando, J. Jelline, R. L. Johnson. Nanoalloys: from theory to applications of alloy clusters and nanoparticles, Chem. Rev., 108, 845-910 (2008).

J. Xiang, S. H. Wei, X. H. Yan, J. Q. You, Y. L. Mao. A density-functional study of Al- doped Ti clusters: TinAl (n = 1-13), J. Chem. Phys., 120, 4251 (2004).

S. Y. Wang, W. Duan, C. Y. Wang. First-principles investigation into the structural stability of icosahedral Ti12X clusters (X = B, C, N, Al, Si, P, V, Cr, Mn, Fe, Co and Ni), J. Phys. B: At. Mol. Opt. Phys., 35, 4015 (2002).

V. V. Alexey, H. Matthias, V. Y. Alexander, V. S. Andrey. Characterization of small pure and Ni-doped titanium clusters: ab initio versus classical approaches, Computational Materials Science, 76, 80-88 (2013).

H. Wang, N. Hu, D. -J. Tao, Z. -H Lu, J. Nie, X. -S. Chen. Structural and electronic properties of phosphorus-doped titanium clusters: A DFT study, Computational and Theoretical Chemistry, 977, 50-54 (2011).

M. J. Frisch and et al. Gaussian 03 (Revision E.01), Gaussian, Inc., Wall (2008).

J. P. Perdew and J. Wang. Accurate and simple

analytic representation of the electron-gas correlation energy, Phys. Rev. B, 45, 13244 (1992).

J. J. Zhao, Q. Qiu, B. L. Wang, J. L. Wang, and G. H. Wang. Geometric and electronic properties of titanium clusters studied by plane-wave ultrosoft pseudopotential, Solid State Commun., 118, 157 (2001).

M. Castro, S. R. Liu, H. J. Zhai and L. S. Wang. Structural and electronic properties of small titanium clusters: an anion photoelectron spectroscopy and density functional study, J. Chem. Phys., 118, 2116 (2003).

T. J. D. Kumar, P. F. Weck, and M. Balakrishnan. Evolution of small Ti clusters and the dissociative chemisorption of H2 on Ti, J. Phys. Chem. C, 111, 7494 (2007).

C. Sosa, J. Andzelm, B. C. Elkin, E. Wimmer, K. D. Dodds, and D. A. Dixon. A local density functional study of the structure and vibrational frequencies of molecular transition-metal compounds, J. Phys. Chem., 96, 6630 (1992).

A. Anderson. Structures, binding energies, and charge distributions for two to six atom Ti, Cr, Fe, and Ni clusters and their relationship to nucleation and cluster catalysis, J. Chem. Phys., 64, 4046 (1976).

M. S. Villanueva and et al. Stable Tin (n = 2-15) clusters and their geometries: DFT Calculations, J. Phys. Chem. A, 110, 10274 (2006).

S. H. Wei, Z. Zeng, J. Q. You, X. H. Yan, X. G. Gong. A density-functional study of small titanium clusters, J. Chem. Phys., 113, 11127 (2000).

Z. H. Lu, J. X. Cao. First-principles calculations for titanium monoxide clusters TinO (n = 1-9), Chin. Phys. B, 17, 3336 (2008).

J. G. Du, X. Y. Sun, J. Chen, G. Jiang. The changes in the geometrical, electronic and magnetic properties of titanium clusters as one titanium atom is substituted by boron, J. Phys. B: At. Mol. Opt. Phys., 43, 205103 (2010).


  • There are currently no refbacks.