Wave Function Analysis of The X Ray Diffraction Experiment

Wave function analysis of the XRay diffraction experiment
C. Frishberg Citation: AIP Conference Proceedings 140, 136 (1986); doi: 10.1063/1.35616 View online: http://dx.doi.org/10.1063/1.35616 View Table of Contents: http://scitation.aip.org/content/aip/proceeding/aipcp/140?ver=pdfcov Published by the AIP Publishing
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WAVE FUNCTION ANALYSIS OF THE X-RAY DIFFRACTION EXPERIMENT C. Frishberg School of Theoretical and Applied Science Ramapo College Mahwah, N.J. 07430 ABSTRACT Current techniques of X-ray crystallography are capable of producing highly accurate electronic densities. Such an electron density should be able to describe the bonding in the crystal and must be consistent with quantum mechanics. We have previously presented a method to obtain a single determinant wave function for the unit ceil of a crystal which closely reproduces the structure factors of the experiment[I-4]. The imposition of the physical requirement that the electron density be related to a single determinant wavefunction reduces the number of independent parameters to be determined for a given system and alleviates the problem of correlated parameters. Furthermore, it permits the calculation of all equilibrium molecular properties and the analysis of the system in terms familiar to chemists. In this paper we review the formalism and results for several atoms and beryllium metal, with an eye to its application to boron and related systems9 INTRODUCTION The fundamental equation for the diffraction of X- rays by crystals,
F(K) =
f ,G)o
(1)
clearly illustrates the relationship between the electron density of the unit cell, p(r), and the experimental structure factors, F(K). The most general way to write an electron density is by expansion in a suitably chosen basis set:
p6) =
1,J
eij ,i(;> *i(h
(2)
In this paper we will assume that all experimental factors that affect the measurement of the structure factors but are not explicitly expressed in Eq. (1) can be accurately accounted for. Furthermore, if we can separate the effects of the vibrational motion of the nuclei from the thermally smeared electron density in
0094-243X/86/1400136-653.00 Copyright 1986 American Institute of Physics
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Eq. (1), then the average electron positions in the static density should be accessible via this experiment. Although the correct way to express temperature factors when using Eq. (2) is not trivial, we have discussed it elsewhere and will not pursue this topic here[5]. It has long been accepted that current levels of accuracy achieved by X-ray diffraction experiments demand analyses of the charge density that go further than the traditional superposition of isolated, spherical atoms[6]. Knowledge of the weighting coefficients, Pij, in Eq. (2), however, imply more information than the electron density alone. This is the charge and bond order matrix (1-matrix) of theoretical calculations. A 1-matrix, the first order reduced density matrix, is obtained from a wavefunction according to
p(I,1') = 2, 3 ... N ) ~(1, 2, 3 ... N) dv 2 ... dv N (3)
Summing over spin variables in p(1,1') will result in p ( r , r ' ) , its spin.less counterpart. The electron density, p(r),is simply p(r, r') evaluated at r ~ = r. Due to the antisymmetry of the wavefunction, p(r, r t) is sufficient to calculate any one-body property such as the kinetic energy or dipole moment. When the basis set is chosen to be that of nucleus-centered atomic orbitals, the P- matrix, as defined by Eq. (2), leads easily to the analysis of the system in terms familiar to chemists. In the following we will show that indeed these coefficients can be found from the X-ray diffraction experiment. We must first consider what properties such an experimentally determined P-matrix should have. Any physically acceptable electron density must obey the rules of quantum mechanics. In particular it must be related via Eq. (3) to an N-body wavefunction that is antisymmetric with respect to interchanging the coordinates of any 2 electrons, as required by the Pauli Principle. Such an electron density is said to be N- representable[7] and will be everywhere positive. However for the interpretation of the elements Pij as the charge and bond order matrix, this requirement is more stringent, viz, tile eigenvalues of P must be bounded by 0 and 1, the N-representability conditions for p(1, 1~) [7]. If one attempts to fit the elements of the P-matrix to reproduce experimental properties, e.g. diffraction intensities, without an explicit effort to ensure the conditions necessary and sufficient for N- representability, the most likely result will be a non- physical electron density. Such densities can have regions of negative probability and are in no way to be compared to a P-matrix calculated theoretically[8]. A class of N-representable P-matrices are the idempotent P-matrices, that is, those that satisfy
p2 = p (4)
Such matrices come from wavefunctions that are single Slater determinants. Although in general one cannot go from a 1-matrix back to the wavefunction,
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the idempotent 1-matrix does allow you to do sol9]. This is the only case for which knowledge of the P-matrix is sufficient to define the full N-body wavefunction. Although single Slater determinants are wave functions for which there is no electron correlation, Gilbert[10] and Harriman[ll] have shown that idempotent density matrices yield electron densities that can exactly describe the electron density of a correlated system. That is to say that using an idempotent P-matrix is not a restriction to densities of single Slater determinants. This point will be illustrated in the next section. Thus we seek a normalized, hermitian, idempotent P- matrix that will best reproduce a set of X-ray diffraction structure factors according to
Fcalc (~) = ~ . Pij

1J
(5)
in a least squares sense. There may in principle be an infinite number of idempotent P-matrices that will correspond to vastly different wavefunetions yet identical electron densities so that x-ray structure factors alone cannot distinguish between them. One problem that plagued early charge density studies using the form of Eq. (1) is that of the high correlation of parameters that are products of atomic basis functions[12]. In this regard the requirement of idempotency imposes physical constraints in addition to the fitting to structure factors that alleviates a good deal of the correlation. When the constraints of orthogonality and normalization of the orbitals are taken into account, the number of "free" parameters in a determinantal wavefunction of N orbitals expanded in m basis functions is N(m-N)[13]. Any single determinant forced to obey this number of constraints should be unambiguously determined. In the systems we have treated using finite basis sets, we have thus far not encountered problems of multiple solutions. We have described the computational methods used for finding such matrices in detail elsewhere[3,4,14]. In the next sections we describe the results of applying the idempotent P-matrix model to a few systems. Li AND Be ATOMS The lithium and beryllium atoms were treated with this approach[14] using theoretical X-ray structure factors calculated by Benesch and Smith[ 15] for the highly accurate CI wavefunctions of Larsson(Li)[16] and Weiss(Be)J17]. The fits to the scattering factors were reduced in each case by a factor of 1000 over the near Hartree-Fock(HF) wavefunctions of Clementi[18] as measured by e , e= E I Fcalc(K) - F(K) I (6)
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Most density dependent properties, for example, < l / r > and < r > showed improvement over H F values, as did the kinetic energies, a property which depends on p(r, r') and not on the density alone. In Table 1 we list some of these properties for the Be atom. Total energies increased somewhat as expected since by definition the Hartree-Fock wavefunction is the single Slater determinant with lowest energy. The increases were less than 0.01% of the total energy indicating a physically reasonable wavefunction. These results show that indeed an idempotent P-matrix can describe the electron density of correlated systems with extraordinary accuracy and give an excellent approximation to properties of more than one electron.
Table 1. Beryllium atom properties. Exact Hartree-Fock[ 18] X-ray Fitted[ 14]
(a.Ll.)
< r -2 > < r -1 > < r > < r2 > < P > <K.E.> <- E> 57.59326 8.42474 5.98812 16.32577 57.01214 14.65763 14.66090 57.62535 8.40878 6.12890 17.32008 63.16368 14.57299 14.57302 57.62659 8.42541 5.98779 16.32169 56.96641 14.59266 14.57150
BERYLLIUM METAL The L C A O formalism presented here is most suitable to the description of molecular crystals. That is where interactions between unit ceils are weak and one can feel secure in interpreting a wavefunction for that entity. Nonetheless we have also found this approach useful for treating beryllium metal[19]. BeryUium crystal has almost an ideal hexagonal close-packed structure with 2 atoms in a centrosymmetric unit cell. Writing the standard crystallographic structure factor for such a unit cell but replacing the atomic density with one as in Eq. (1) using an idempotent P-matrix, is a first approximation to the wavefunction for this extended system. This one-center model is equivalent to describing the beryllium crystal as a sum of non-interacting, non- spherical, hybridized beryllium atoms. In this calculation, the core electrons were not permitted to vary but were kept fixed at Huzinaga's[20] free atom Be (ls) 2 core. Two functions were chosen for the valence basis set. The first is a sum of spherical gaussians centered on the Be atom representing a 2s orbital and the
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second was a sum of 12 spherical gaussian orbitals permitted to float off the atomic center in a manner consistent with the D3h site symmetry. When normalization is taken into account the valence P-matrix has only 1 parameter to be determined by least squares fitting to the structure factors along with 3 thermal parameters, the position of the floaters, overall scale factor and exponential factor of the floating gaussians. The diffraction data used was that obtained by Larsen and Hansen[21]. The least square fit gives RWF = 0.0018. Thermal parameters agree closely with that determined by neutron diffraction[21]. It is found that charge flows from nuclear regions and octahedral channels into tetrahedral hole regions. The deformation density of the crystal agrees quantitatively with the experimental deformation density of Larsen and Hansen. It shows a charge buildup along the c-axis which is consistent with the fact that the crystal's c / a ratio is about 3% below the ideal value for hexagonal close packing indicating somewhat stronger bonding along this axis. A valence density map agrees qualitatively with the ab initio calculations of Dovesi, et.al.[22] and Chou, et.al.[23] and gives results intermediate between the two calculations. Extension of this work to account for the metallic behavior of beryllium involves the use of Wannier orbitals which can be used in conjunction with the requirement of idempotency [24]. APPLICATION TO BORON AND BORON COMPOUNDS The unusual properties of crystalline boron and related compounds provides the motivation for a greater understanding of their electronic structures. Given the small number of unique atoms per unit cell and the availability of high quality X-ray diffraction work, these systems are quite amenable to analysis via the idempotent P-matrix model. Application of the one-center model as was used in the study of beryllium metal is straightforward and requires no preconceived notion of the nature of the bonding involved, other than adherence to the site symmetry. This is an important point since boron and its compounds often defy the rules of classical bonding theory. Even at this level of approximation we can hope to obtain an excellent charge density and onebody properties, as well as the hybridizations of the atoms.
REFERENCES 1. W. Clinton, C. Frishberg, L. Massa and P. Oldfield, Int. J. Quantum Chem. Symp. 7_, 505 (1973). 2. W. Clinton and L. Massa, Phys. Rev. Lett., 2 0 , 1 3 6 3 (1972). 3. C. Frishberg and L. Massa, Int. J. Quantum Chem., X I I I , 801 (1978). 4. C. Frishberg and L. Massa, Acta Cryst., A 3 8 , 9 3 (1982).
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5. W. Clinton, C. Frishberg, M. Goldberg, L. Massa, and P. Oldfield, Int. J. Quantum Chem., Syrup.17,517 (1983). 6. See for example, P. Coppens in "Electronic Structure of Polymers and Molecular Crystals", J.M. Andre and J. Ladik, eds., Plenum, N.Y. (1975) 7. A. Coleman, Rev. Mod. Phys., 35,3,668 (1963). 8. C. Frishberg, Ph.D. thesis, City University of New York, 1975. 9. P.O. Lowdin, Phys. Rev., 97,147 (1955). 10. T. Gilbert, Phys.Rev., B12,2111 (1975). 11. J. Harriman, Phys. Rev., A24,2,680 (1981). 12. P. Coppens, T. Willoughby and L. Csonka, Science, 167,1126 (1970). 13. W. Clinton, A. GaUl, and L. Massa, Phys. Rev., 177,1, 7 (1969). 14. C. Frishberg and L. Massa, Phys. Rev., B24,12 (1981). 15. R. Benesch and V. Smith, Jr., J. Chem. Phys., 53,1466 (1970); R. Benesch and V. Smith, Jr., Acta Cryst. A26,586 (1970). 16. S. Larsson, Phys. Rev., 169,49 (1968). 17. A. Weiss, Phys. Rev., 122,1326 (1961). 18. E. Clementi, IBM J. Res. Dev. _9(1965). 19. L. Massa, M. Goldberg, C. Frishberg, S. LaPlaca, and R. Boehme, to be published in Phys. Rev. Lett. 20. S. Huzinaga, J. Chem. Phys., 42,4, 1293 (1965). 21. F. Larsen and S. Hansen, Acta Cryst. B40,169 (1984). 22. R. Dovesi, C. Pisani, F. Ricca and C. Roetti, Phys. Rev. B25,3731 (1982). 23. M. Chou, P.Lam and M. Cohen, Phys. Rev. B28,4179 (1983). 24. M. Goldberg and L. Massa, Int. J. Quantum Chem., XXIV, 113 (1983).

Wave Function Analysis of The X Ray Diffraction Experiment

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Wave function analysis of the XRay diffraction experiment

eij ,i(;> *i(h

Fcalc (~) = ~ . Pij

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