TY  - JOUR
AU  - Saloni, J.
AU  - Roszak, S.
AU  - Hilpert, K.
AU  - Popovic, A.
AU  - Miller, M.
AU  - Leszczynski, J.
TI  - Mass spectrometric and quantum chemical studies of the thermodynamics and bonding of neutral and ionized LnCl, LnCl2, and LnCl3 species (Ln=Ce, Lu)
JO  - Inorganic chemistry
VL  - 45
SN  - 0020-1669
CY  - Washington, DC
PB  - American Chemical Society
M1  - PreJuSER-57483
SP  - 4508 - 4517
PY  - 2006
N1  - Record converted from VDB: 12.11.2012
AB  - The mass spectral patterns of CeCl3(g) and LuCl3(g) and appearance energies for the identified ions were measured using a Nier-type mass spectrometer coupled with a Knudsen cell. The molecular ion CeCl3+ was found to be considerably less stable in comparison to LuCl3+. Partial pressures and sublimation enthalpies of LnCl(3)(s) to monomeric LnCl(3)(g) and dimeric Ln(2)Cl(6)(g) species were obtained in the ranges of 882-1028 (Ln = Ce) and 850-1004 K (Ln = Lu). The contribution of dimeric Ce2Cl6(g) species to equilibrium vapors of CeCl3(s) is considerably smaller than the Lu2Cl6(g) contribution in LuCl3(s) vapors. The measurements were supplemented by quantum chemical ab initio studies of structures, energetics, and vibrational frequencies of neutral and singly ionized LnCl, LnCl(2), and LnCl(3) species (Ln = Ce, Lu). The theoretical appearance energies of different ions, calculated from the energies of the gaseous species, are in good agreement with experimental data. The fragmentation energies of LnCl, LnCl(2), and LnCl(3) were also computed and compared with the mass spectral patterns of respective vapor species. The Mulliken and natural bond orbital electron population methods were applied for the systematic analysis of the bonding scheme in molecules and cations.
KW  - J (WoSType)
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000237690700033
DO  - DOI:10.1021/ic051205h
UR  - https://juser.fz-juelich.de/record/57483
ER  -