Abstract
The geometrical parameters of lanthanum and lutetium trihalide dimer molecules Ln2X6 (Ln = La, Lu; X = F, Cl, Br, I) and dissociation energies of Ln2X6 → 2LnX3 were calculated in terms of Mö ller-Plesset fourth order perturbation theory including single, double, triple, and quadruple excitations (SDTQ-MP4). Variation of the properties of molecules in series of compounds Ln2F6 → Ln2Cl6 → Ln2Br6 → Ln2I6 from lanthanum La2X6 to lutetium Lu2X6 compounds and from monomer LnX3 to dimer Ln2X6 molecules has been studied (the parameters of LnX3 molecules were determined in the same SDTQ-MP4 approximation). The lanthanide compression of the metal-halogen internuclear distance Δr(Ln-X) = r e(La-X)-r e(Lu-X) depends on the nature of the ligand X and coordination number of Ln. The calculated data are compared with previously published experimental and theoretical data on the structure and dissociation energies of Ln2X6 molecules.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
V. G. Solomonik and O. Yu. Marochko, Zh. Strukt. Khim., 41, No. 5, 885–895 (2000).
V. G. Solomonik and O. Yu. Marochko, Zh. Fiz. Khim., 74, No. 12, 2296–2298 (2000).
V. G. Solomonik, “Potential energy surfaces of low-lying nearly degenerate spin-orbit states of cerium trihalide molecules,” Book of Abstracts, 20th Austin Symposium on Molecular Structure, Texas University, Austin, TX, USA (2004).
V. G. Solomonik, A. N. Smirnov, and M. A. Mileev, Koordinats. Khim., 31, No. 3, 218–228 (2005).
A. Granovsky, http://classic.chem.msu.su/gran/gamess/index.html.
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, et al., J. Comput. Chem., 14, No. 11, 1347–1363 (1993).
M. J. Stevens, H. Basch, and M. Krauss, J. Chem. Phys., 81, No. 12, 6026–6033 (1984).
M. J. Stevens, M. Krauss, H. Basch, et al., Can. J. Chem., 70, No. 2, 612–630 (1992).
T. R. Cundari and W. J. Stevens, J. Chem. Phys., 98, No. 7, 5555–5565 (1993).
S. F. Boys and F. Bernardi, Mol. Phys., 19, 553 (1970).
A. Kovacs, Chem. Phys. Lett., 319, 238–246 (2000).
N. I. Giricheva, G. V. Girichev, A. V. Krasnov, et al., Zh. Strukt. Khim., 41, No. 3, 480–488 (2000).
J. A. Roberts and A. W. Searcy, High Temp. Sci., 4, No. 5, 411–422 (1972).
C. Hirayama, G. L. Carlson, P. M. Castle, et al., J. Less-Common Met., 45, No. 2, 293–300 (1976).
A. M. Pogrebnoi, L. S. Kudin, A. Yu. Kuznetsov, Rapid Commun. Mass Spectr., 11, 1536–1546 (1997).
L. S. Kudin, A. M. Pogrebnoi, and G. G. Burdukovskaya, Zh. Fiz. Khim., 77, No. 6, 977–984 (2003).
L. S. Kudin and D. E. Vorob’yov, ibid., 79, No. 8, 1395–1399 (2005).
L. S. Kudin, V. G. Solomonik, L. N. Gorokhov, et al., Reports on RFBR grant No. 01-03-32194a “ Investigations of the structure, energies, and reactivities of lanthanide trichlorides by high-temperature mass spectrometry and ab initio quantum-chemical methods” (2001–2003).
Author information
Authors and Affiliations
Additional information
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp. 1013–1018, November–December, 2005.
Original Russian Text Copyright © 2005 by V. G. Solomonik and A. N. Smirnov
Rights and permissions
About this article
Cite this article
Solomonik, V.G., Smirnov, A.N. Structure and energy stability of lanthanum and lutetium trihalide dimer molecules. J Struct Chem 46, 973–978 (2005). https://doi.org/10.1007/s10947-006-0230-y
Received:
Issue Date:
DOI: https://doi.org/10.1007/s10947-006-0230-y