Correlation-induced corrections to the band structure of boron nitride: a wave-function-based approach

We present a systematic study of the correlation-induced corrections to the electronic band structure of zinc-blende BN. Our investigation employs an ab initio wave-function-based local Hamiltonian formalism which offers a rigorous approach to the calculation of the polarization and local charge redistribution effects around an extra electron or hole placed into the conduction or valence bands of semiconducting and insulating materials. Moreover, electron correlations beyond relaxation and polarization can be readily incorporated. The electron correlation treatment is performed on finite clusters. In conducting our study, we make use of localized Wannier functions and embedding potentials derived explicitly from prior periodic Hartree-Fock calculations. The on-site and nearest-neighbor charge relaxation bring corrections of several eV to the Hartree-Fock band gap. Additional corrections are caused by long-range polarization effects. In contrast, the dispersion of the Hartree-Fock bands is marginally affected by electron correlations. Our final result for the fundamental gap of zinc-blende BN compares well with that derived from soft x-ray experiments at the B and N K-edges.Comment: 18 pages, 8 figures; the following article has been submitted to J. Chem. Phy

Electronic, Optical, Structural, and Elastic Properties of MAX Phases and (Cr2Hf)2Al3C3

Title from PDF of title pages, viewed on July 13, 2015Dissertation advisor: Wai-Yim ChingVitaIncludes bibliographic references (pages 124-140)Thesis (Ph.D.)--Department of Physics and Astronomy and Department of Chemistry. University of Missouri--Kansas City, 2015The term “MAX phase” refers to a very interesting and important class of layered ternary transition-metal carbides and nitrides with a novel combination of both metal- and ceramic-like properties that have made these materials highly regarded candidates for numerous technological and engineering applications. In the present dissertation work, the electronic structure and optical conductivities of 20 MAX phases Ti3AC2 (A = Al, Si, Ge), Ti2AC (A = Al, Ga, In, Si, Ge, Sn, P, As, S), Ti2AlN, M2AlC (M = V, Nb, Cr), and Tan+1AlCn (n = 1 to 4) are studied using the first-principles orthogonalized linear combination of atomic orbitals (OLCAO) method. It is confirmed that the N(Ef) (total density of states at the Fermi level Ef) increases as the number of valence electrons of the composing elements increases. The local feature of total density of states (TDOS) near Ef is used to predict structural stability. The calculated effective charge on each atom shows that the M (transition-metal) atoms always lose charge to the X (C or N) atoms, whereas the A-group atoms mostly gain charge but some lose charge. Bond order values are obtained and critically analyzed for all types of interatomic bonds in the 20 MAX phases. Also included in this work is the exploration [using (Cr2Hf)2Al3C3 as an example] of the possibility of incorporating more types of elements into a MAX phase while maintaining the crystallinity, instead of creating solid solution phases. The crystal structure and elastic properties of (Cr2Hf)2Al3C3 are studied using the Vienna ab initio Simulation Package. Unlike MAX phases with a hexagonal symmetry (P63/mmc, #194), (Cr2Hf)2Al3C3 crystallizes in the monoclinic space group of P21/m (#11). Its structure is found to be energetically much more favorable against the allotropic segregation and solid solution phases. Calculations using a stress versus strain approach and the VRH approximation for polycrystals also show that (Cr2Hf)2Al3C3 has outstanding elastic moduliIntroduction of max phases -- Scope and motivation of research -- Theory and methodology -- Results and discussion on the twenty max phases -- Results and discussion on the derivative (Cr2Hf)2Al3C3 -- Summary -- Appendix A. Full basis of titanium atomic orbitals -- Appendix B. The relaxed unit cell of (Cr2Hf)2Al3C3 -- Appendix C. The relaxed 1 x 1 x 3 supercell of (Cr2Hf)2Al3C3 -- Appendix D. The relaxed segregation model -- Appendix E. The relaxed 3 x 3 x1 supercell of (Cr2Hf)2Al3C3 -- Appendix F. The relaxed solid solution mode

Wavefunction-based method for excited-state electron correlations in periodic systems - application to polymers

A systematic method for determining correlated wavefunctions of extended systems in the ground and excited states is presented. It allows to fully exploit the power of quantum-chemical programs designed for correlation calculations of finite molecules. Using localized Hartree-Fock (HF) orbitals (both occupied and virtual ones), an effective Hamiltonian which can easily be transferred from finite to infinite systems is built up. Correlation corrections to the matrix elements of the effective Hamiltonian are derived from clusters. To treat correlation effects, multireference configuration interaction (MRCI) calculations with singly and doubly excited configurations (SD) are performed. This way one is able to generate both valence and conduction bands where all correlation effects in the excited states as well as in the ground state of the system are taken into account. An appropriate size-extensivity correction to the MRCI(SD) correlation energies is developed which takes into account the open-shell character of the excited states. This approach is applicable to a wide range of polymers and crystals. In the present work trans-polyacetylene is chosen as a test system. The corresponding band structure is obtained with the correlation of all electrons in the system being included on a high level of sophistication. The account of correlation effects leads to substantial shifts of the "center-of-mass" positions of the bands (valence bands are shifted upwards and conduction bands downwards) and a flattening of all bands compared to the corresponding HF band structure. Further an extention of the above approach to excitons (optical excitations) in crystals is developed which allows to use standard quantum-chemical methods to describe the electron-hole pairs and to finally obtain excitonic bands.Comment: 111 pages, 23 figures, Ph.D. Thesi