Introduction I will present an example of first principles study of electric field gradients in pure, cubic HfV2 and ZrV2

Laves phases and supercell calculations with Ta and Cd impurities. Results are compared with the existing experimental data from time differential perturbed angular correlations measurements of mentioned probe atoms. Calculations are performed using all-electrons augmented plane waves plus local orbitals (APW + lo) formalism as implemented in Wien2k, which is a computational code based on density functional theory. Motivation Electric field gradient is a quantity which depends on the electronic charge distribution in the vicinity of the observed nucleus, as well as the nearest neighbor distance and their distribution. This makes it a powerful tool for electron density investigation, a physical quantity which is a direct consequence of the chemical composition of the material. One of the experimental techniques used to study EFG is the time differential perturbed angular correlation spectroscopy. Others, more familiar so to say, are NMR or Moss spectroscopy. Interpretation of the experimental results can be often complicated, because the atomic position of the probe atoms in the crystal lattice is unknown. At this point, it is convenient to calculate the EFGs of probe atom on different atomic positions and to compare these values with measured ones. If the measured and calculated values are comparable one can with great certainty determine the probe atom position, site symmetry, and crystallographic structure or even spin state of the atom of interest. Also, it should be pointed out that in mentioned experiments the sign of EFG tensors is barely established, but it can be easily determined using these calculations. PAC basic principle The PAC spectroscopy is a nuclear technique used to obtain information on the microstructure of solids through the investigation of quadrupole interactions. Characterization of the materials is based upon the interaction of radioactive probe nuclei with its direct surroundings in the crystal lattice. Or, more precise, the interaction of nuclear quadruple moment of probe atom and electric field created by the local electronic cloud. Atomic probes that are used are 181Hf and 111In due to their favorable characteristics, well defined anisotropic gamma ray cascades, large nuclear moments, and relatively long lifetimes of intermediate state. These probes exhibit radioactive decay into 181Ta and 181Cd which are then considered as impurities in crystal lattice. Why Laves phases? Laves phases form the largest group of intermetallic compounds which are of great technological interest due to their remarkable mechanical and physical properties. They are known by their high melting temperatures, high strength and excellent oxidation resistance; also they exhibit great ability to absorb hydrogen. Because of the mentioned qualities they are used under extreme conditions, and are considered as the potential materials for Hydrogen storage. These particular compounds are also known by their superconductivity.

Structural information

Above 120 K both studied compounds are cubic C15 Laves phases, with Fd-3m space group. Hf and Zr occupy a cubic atomic position, while the V is located at the noncubic atomic site. Therefore, because of the cubic symmetry Hf and Zr have 0 EFG. In order to calculate the effect of impurities on EFG, 2x2x2 supercells were constructed from the starting unit cells. Ta or Cd is introduced into these cells, and they substituted all nonequivalent atomic sites. During these calculations it was necessary to keep impurity atom surrounding identical as in the original unit cell. Calculation details Here are given only a few of many, very important calculation parameters defined within wien2k. They are not picked randomly, but carefully tested for every required value, in this example it would be EFG. Muffin-tin spheres are nonoverlapping spheres centered at the atomic nucleus were set for every atom, to be 2.3 bohr for Hf and Ta, 2.2 bohr for Zr nd Cd, and for V 2.1 bohr. Plane wave cutoff parameter determines the number of basis functions used and it had different values for cubic and supercells. (it was chosen to be 7.0 and 8.5) Another parameter is the cutoff energy between the core and the valence states -6.0 Ry with every state being much localized within its classification. The exchange and correlation effects, which are in DFT both included approximately, were taken into account by the generalized gradient approximation (GGA). In our calculations the self-consistency was achieved by demanding that the convergence of the integrated charge difference between two successive iterations was less than 10-5 electron. Results The investigated structures were relaxed until the forces acting on atoms were less than 1 mRy/bohr. Their volume was optimized and Murnaghans equation of state was used for further extraction of optimal lattice parameters, which are presented in this table. Here are given calculated values of structural parameters of pure compounds, compared with existing values form X-ray diffraction measurements, and previously conducted calculations. Values given are in fair agreement. In the second table are presented distances between Hf, or Zr and their nearest neighbour as well as the distance between V and its NN before and after volume optimization. In both cases distances decreased as a result of the decrease in volume. In the next table are presented calculated distances from impurity atoms to its nearest neighbor, in this case V, for the relaxed and nonrelaxed structure. When impurity substituted Hf or Zr distances remained unchanged, while when they substituted V it gave mixed results. Here are the results of main part of the present calculations, EFG values. This part of calculations follows the structure optimization. First are given EFGs of pure HfV2 and ZrV2. They have identical order of magnitude, but are opposite in sign. Considering that for both compounds contributions from p and d electrons are comparable and of the opposite sign, resulting EFGs are close to zero. Results of EFG calculations on Impurity are presented in table 5. Unfortunately, only comparison with experimental values can be made in the case of Hf compound with Cd and Ta impurity. It can be seen that our values and experimental values are almost identical. This serves as a confirmation that Cd probe substituted V atom, while Ta substituted Hf. Considering that no

experimental values for Zr compound are existent one cannot with great certainty determine substitution site of Ta or Cd. For both impurities in Hf compound and for Cd impurity in ZrV2 major contribution to EFG comes from p-type electrons, while others can be almost neglected. Only in the case of Ta in Zr compound contributions are comparable. Summary To summarize, here I have presented an example of the first principles calculations of the fully relaxed ZrV2 and HfV2 structure. This gave the small insight into the required calculation parameters, very small insight of electronic and structure properties of these intermetallic compounds. Ive shown that the values of EFGs in these two compounds are of the same order of magnitude, with the different major contribution, which was expected. Also, the calculated EFGs at Cd and Ta impurities in Hf intermetallic exhibited fair agreement with the existing experimental values. This enabled us to determine the atomic position of the used probe atoms and major contribution to the overall EFG value. Like I said, unfortunately, no TDPAC experiments were conducted on ZrV2 therefore no comparison can be made, but one can assume that the trend will follow considering that Hf and Zr are isoelectronic, and have similar behaviour as pure cubic systems.