Variational thermodynamic calculations for some liquid sd metals

1986 ◽  
Vol 64 (1) ◽  
pp. 75-83 ◽  
Author(s):  
D. H. Li ◽  
R. A. Moore ◽  
S. Wang

A tractable and reliable expression for the one valence-electron eigenenergies, required in calculating the total energy of a disordered sd-type metal, is formulated in the context of the model-potential theory. With the aid of this expression, the variational calculation of the Helmholtz free energy using the hard-sphere model as a reference system, as employed in ab initio calculations of the thermodynamic properties for the nearly-free-electron-like (NFE) liquid metals, can now be extended with reasonable accuracy to those liquid sd metals in which the d-like valence-electron states below the Fermi level are not very localized. Also, the ab initio-type pseudopotential calculation of the interionic pair potentials, as carried out for the NFE-like metals in the literature, is made practical for these sd metals in their disordered states.

1986 ◽  
Vol 64 (7) ◽  
pp. 852-856 ◽  
Author(s):  
D. H. Li ◽  
R. A. Moore ◽  
S. Wang

A procedure employing a generalized, nonlocal, model-pseudopotential theory for the calculation of the total valence-electron energy in liquid metals was presented earlier and shown to be suitable for use in a variational calculation of the Helmholtz free energy, and hence also for other properties, of sd and the early 3d transition metals. In the first part of this paper we show that the same procedure also works well for the first four of the 4d transition metals. However, the accuracy of the calculations decreases with increasing number of d-like valence electrons. This is attributed to narrow valence d bands. Thus, in the second part of this paper we revise and generalize the earlier procedure to consider explicitly the localization of some of the d-like valence electrons on the ions. The validity of the revisions is shown by calculating a number of the properties of liquid metallic Cr, Mn, and Fe.


1987 ◽  
Vol 40 (4) ◽  
pp. 751 ◽  
Author(s):  
JB Peel ◽  
EI Vonnagyfelsobuki

The HeI and HeII photoelectron spectra of the chloro toluenes have been measured. The spectra are assigned using HeI/HeII cross-section ratios and a composite-molecule model within an ab initio valence-electron-only model potential (VEOMP) framework. The order of the first two ionization potentials for the chloro toluenes is assigned as πS < πA which is contrary to the VEOMP assignment for benzal chloride and benzotrichloride , but is consistent with linear correlations using group electronegativities and σI scales. Furthermore, linear correlations using the first two ionization potentials of fluoro and chloro toluenes with group electronegativities are shown to be a useful aid in spectral assignment and, moreover, suggest that for benzyl fluoride and benzal chloride the most appropriate σI values are 0.20 and 0.31 respectively.


1970 ◽  
Vol 1 (12) ◽  
pp. 4850-4851 ◽  
Author(s):  
Charles J. Vadovic ◽  
C. Phillip Colver

2007 ◽  
Vol 353 (32-40) ◽  
pp. 3523-3527 ◽  
Author(s):  
E. Chacón ◽  
P. Tarazona ◽  
J.A. Vergés ◽  
M. Reinaldo-Falagán ◽  
E. Velasco ◽  
...  

2002 ◽  
Vol 17 (3) ◽  
pp. 165-172 ◽  
Author(s):  
Y. Le Page ◽  
John R. Rodgers ◽  
Peter S. White

There are 39 CRYSTMET® entries in the hexagonal space group P-3m1 (164) reporting both distinct pure phase compounds and atomic coordinates. Having the same Wyckoff positions in the same space group as the C6 structure type, all are isopointal with it. The range of observed c/a values extends from about 0.65 to 1.83. Three types are distinguished: Layered materials with CdI2 type, the CeCd2 type which is a slight distortion of the hexagonal AlB2 type, and the intermediate EuGe2 type made of the materials AuTe2, BaSi2, EuGe2, and SrGe2. Ab initio modeling of the 26 entries with CdI2 and EuGe2 type and atomic coordinates reproduces convincingly both their c/a axial ratios and z coordinates. For CoO2 and SiTe2, both c/a and z deviate to a degree from the reported values, indicating that those materials should be reexamined for superstructures, stoichiometry, etc. Ab initio modeling of the 11 cell-and-type entries with CdI2 type and no coordinates in CRYSTMET reproduced convincingly their reported axial ratios. The X-ray cell data and the ab initioz coordinates were then used in the production of reliable calculated powder patterns for CoTe2, CrSe2, HfS2, HfSe2, HfTe2, NbTe2, SnSe2, VS2, VTe2, ZrS2, and ZrTe2. All 11 patterns have been inserted in the intense diffraction line search system of CRYSTMET operated under the Materials Toolkit. Comparison of calculated patterns for SnSe2 and ZrTe2 with experimental entries in the PDF exposes the complementarity of calculated and experimental powder patterns and suggests that JCPDS pattern #15-223 should be reinterpreted in terms of the CdI2 structure type. The CeCd2⇔AlB2 type transformation is modeled and discussed on YCd2 using both ab initio methods and a hard-sphere model. For z<0.45, the ab initio solution is identical with that from the hard-sphere model while a quantum regime is predicted in the small region 0.45<z<0.467 beyond which YCd2 abruptly transforms to the AlB2 type. In spite of the new understanding gained, this modeling fell slightly short of allowing calculation of z values and powder patterns for the materials CaHg2, DyHg2, ErCd2, GdHg2, HoCd2, HoHg2, LuCd2, NdCd2, SmHg2, TbCd2, and TbHg2 with no coordinates in CRYSTMET.


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