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Chem Sci ; 10(26): 6508-6518, 2019 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-31341603


A series of trivalent f-block tungstates, MW2O7(OH)(H2O) (M = La, Ce, Pr, Nd, and Pu) and AmWO4(OH), have been prepared in crystalline form using hydrothermal methods. Both structure types take the form of 3D networks where MW2O7(OH)(H2O) is assembled from infinite chains of distorted tungstate octahedra linked by isolated MO8 bicapped trigonal prisms; whereas AmWO4(OH) is constructed from edge-sharing AmO8 square antiprisms connected by distorted tungstate trigonal bipyramids. PuW2O7(OH)(H2O) crystallizes as red plates; an atypical color for a Pu(iii) compound. Optical absorption spectra acquired from single crystals show strong, broadband absorption in the visible region. A similar feature is observed for CeW2O7(OH)(H2O), but not for AmWO4(OH). Here we demonstrate that these significantly different optical properties do not stem directly from the 5f electrons, as in both systems the valence band has mostly O-2p character and the conduction band has mostly W-5d character. Furthermore, the quasi-particle gap is essentially unaffected by the 5f degrees of freedom. Despite this, our analysis demonstrates that the f-electron covalency effects are quite important and substantially different energetically in PuW2O7(OH)(H2O) and AmWO4(OH), indicating that the optical gap alone cannot be used to infer conclusions concerning the f electron contribution to the chemical bond in these systems.

J Phys Condens Matter ; 31(33): 335601, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31067512


We propose an approach that is under the framework of Gutzwiller wave function but goes beyond the commonly adopted Gutzwiller approximation to improve the accuracy and flexibility in treating the correlation effects. Detailed formalism is described for a dimer which is straightforwardly generalized later to more complicated periodic bulk systems. The accuracy of the approach is demonstrated by evaluating the potential energy curves of spin-singlet N2 dimer, spin-triplet O2 dimer, and 1D hydrogen chain. The computational workload of the approach can be easily handled by efficient parallel computing.

J Phys Condens Matter ; 31(19): 195902, 2019 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-30736027


We report benchmark calculations of the correlation matrix renormalization (CMR) approach for 23 molecules in the well-established G2 molecule set. This subset represents molecules with spin-singlet ground state in a variety of chemical bonding and coordination environments. The QUAsi-atomic minimal basis-set orbitals (QUAMBOs) are used as local orbitals in both CMR and full configuration interaction (FCI) calculations for comparison. The results obtained from the calculations are also compared with available experimental data. It is shown that the CMR method produces binding and dissociation energy curves in good agreement with the QUAMBO-FCI calculations as well as experimental results. The CMR benchmark calculations yield a standard deviation of 0.09 Å for the equilibrium bond length and 0.018 Hartree/atom for the formation energy, with a gain of great computational efficiency which scales like Hartree-Fock method.

J Am Chem Soc ; 140(5): 1674-1685, 2018 02 07.
Artigo em Inglês | MEDLINE | ID: mdl-29320850


A series of f-block chromates, CsM(CrO4)2 (M = La, Pr, Nd, Sm, Eu; Am), were prepared revealing notable differences between the AmIII derivatives and their lanthanide analogs. While all compounds form similar layered structures, the americium compound exhibits polymorphism and adopts both a structure isomorphous with the early lanthanides as well as one that possesses lower symmetry. Both polymorphs are dark red and possess band gaps that are smaller than the LnIII compounds. In order to probe the origin of these differences, the electronic structure of α-CsSm(CrO4)2, α-CsEu(CrO4)2, and α-CsAm(CrO4)2 were studied using both a molecular cluster approach featuring hybrid density functional theory and QTAIM analysis and by the periodic LDA+GA and LDA+DMFT methods. Notably, the covalent contributions to bonding by the f orbitals were found to be more than twice as large in the AmIII chromate than in the SmIII and EuIII compounds, and even larger in magnitude than the Am-5f spin-orbit splitting in this system. Our analysis indicates also that the Am-O covalency in α-CsAm(CrO4)2 is driven by the degeneracy of the 5f and 2p orbitals, and not by orbital overlap.

Phys Rev Lett ; 111(19): 196801, 2013 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-24266481


We present zero-temperature first-principles calculations of elemental cerium and we compute its pressure-volume phase diagram within a theoretical framework able to describe simultaneously both the α and the γ phases. A surprising result revealed by our study is the presence of a clear signature of the transition at zero temperature and that this signature can be observed if and only if the spin-orbit coupling is taken into account. Our calculations indicate that the transition line in the pressure-temperature phase diagram of this material has a low-T critical point at negative pressures, placed very close to zero temperature. This suggests that cerium is very close to being "quantum critical," in agreement with recent experiments.

Nanoscale ; 4(8): 2567-70, 2012 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-22437545


Based on density-functional calculation and genetic algorithm structure search, we propose a series of 16-coordinate core-shell clusters: M@Li(16)(M = Ca, Sr, Ba, Ti, Zr, Hf). A tetrahedral (T(d)) structure with an outer shell of 16 lithium atoms and one enclosed heavy atom is found to be the global minimum in the structural exploration of BaLi(16) based on genetic algorithm. This structure also has lower energy compared to the other isomers we employed in all the MLi(16) clusters. In this structure, the atoms are bonded together by metallic bonds with alkali (IA) and alkaline-earth (IIA) metal atoms. Their corresponding first electronic shells are closed with significant energy gaps because their total numbers of valence electrons fulfil the 18-electron rule. Such a combination could be extended to 20-electron systems by enclosing IVB elements. With simple valence electrons and highly symmetric structures, superatomic molecular orbitals are identified in all of the T(d) clusters.