Electron Correlation and the c-axis Dispersion of Cu d_z^2: a New Band Structure for High Temperature Superconductors

Previously we showed the major effect of electron correlation in the cuprate superconductors is to lower the energy of the Cu d_x^2-y^2/O p_sigma (x^2-y^2) band with respect to the Cu d_z^2/O' p_z (z^2) band. In our 2D Hubbard model for La_1.85Sr_0.15CuO_4 (LaSCO), the z^2 band is narrow and crosses the standard x^2-y^2 band just below the Fermi level. In this work, we introduce c-axis dispersion to the model and find the z^2 band to have considerable anisotropic 3D character. An additional hole-like surface opens up in the z^2 band at (0,0,2pi/c) which expands with doping. At sufficient doping levels, a symmetry allowed x^2-y^2/z^2 band crossing along the (0,0)-(pi,pi) direction of the Brillouin zone appears at the Fermi level. At this point, Cooper pairs between the two bands (e.g. (k uparrow x^2-y^2/k downarrow z^2)) can form, providing the basis for the Interband Pairing Theory of superconductivity in these materials.Comment: submitted to Phys. Rev. Lett. Related publications: Phys. Rev. B 58, 12303 (1998); Phys. Rev. B 58, 12323 (1998); cond-mat/9903088; cond-mat/990310

Ab-Initio Calculation of Molecular Aggregation Effects: a Coumarin-343 Case Study

We present time-dependent density functional theory (TDDFT) calculations for single and dimerized Coumarin-343 molecules in order to investigate the quantum mechanical effects of chromophore aggregation in extended systems designed to function as a new generation of sensors and light-harvesting devices. Using the single-chromophore results, we describe the construction of effective Hamiltonians to predict the excitonic properties of aggregate systems. We compare the electronic coupling properties predicted by such effective Hamiltonians to those obtained from TDDFT calculations of dimers, and to the coupling predicted by the transition density cube (TDC) method. We determine the accuracy of the dipole-dipole approximation and TDC with respect to the separation distance and orientation of the dimers. In particular, we investigate the effects of including Coulomb coupling terms ignored in the typical tight-binding effective Hamiltonian. We also examine effects of orbital relaxation which cannot be captured by either of these models

Raman scattering in C_{60} and C_{48}N_{12} aza-fullerene: First-principles study

We carry out large scale {\sl ab initio} calculations of Raman scattering activities and Raman-active frequencies (RAFs) in ${\rm C}_{48}{\rm N}_{12}$ aza-fullerene. The results are compared with those of ${\rm C}_{60}$. Twenty-nine non-degenerate polarized and 29 doubly-degenerate unpolarized RAFs are predicted for ${\rm C}_{48}{\rm N}_{12}$. The RAF of the strongest Raman signal in the low- and high-frequency regions and the lowest and highest RAFs for ${\rm C}_{48}{\rm N}_{12}$ are almost the same as those of ${\rm C}_{60}$. The study of ${\rm C}_{60}$ reveals the importance of electron correlations and the choice of basis sets in the {\sl ab initio} calculations. Our best calculated results for ${\rm C}_{60}$ with the B3LYP hybrid density functional theory are in excellent agreement with experiment and demonstrate the desirable efficiency and accuracy of this theory for obtaining quantitative information on the vibrational properties of these molecules.Comment: submitted to Phys.Rev.

Experimental and Computational Studies of the Kinetics of the Reaction of Atomic Hydrogen with Methanethiol

Article on experimental and computational studies of the kinetics of the reaction of atomic hydrogen with methanethiol