North-South Dialogues in Forced Migration

The following speech was given by Elizabeth McWeeny, President of the Canadian Council of Refugees, on the occasion of the opening of the tenth biennial conference of the International Association of the Study of Forced Migration, hosted by the Centre for Refugee Studies of York University in June 2006

Ab initio Wannier-function-based many-body approach to Born charge of crystalline insulators

In this paper we present an approach aimed at performing many-body calculations of Born-effective charges of crystalline insulators, by including the electron-correlation effects. The scheme is implemented entirely in the real space, using Wannier-functions as single-particle orbitals. Correlation effects are computed by including virtual excitations from the Hartree-Fock mean field, and the excitations are organized as per a Bethe-Goldstone-like many-body hierarchy. The results of our calculations suggest that the approach presented here is promising.Comment: 5 pages, to appear in Phys. Rev. B. (Rapid Comm., Dec 15, 2004

Ab initio Wannier-function-based correlated calculations of Born effective charges of crystalline Li2_{2}O and LiCl

In this paper we have used our recently developed ab initio Wannier-function-based methodology to perform extensive Hartree-Fock and correlated calculations on Li$_{2}$O and LiCl to compute their Born effective charges. Results thus obtained are in very good agreement with the experiments. In particular, for the case of Li$_{2}$O, we resolve a controversy originating in the experiment of Osaka and Shindo {[}Solid State Commun. 51 (1984) 421] who had predicted the effective charge of Li ions to be in the range 0.58--0.61, a value much smaller compared to its nominal value of unity, thereby, suggesting that the bonding in the material could be partially covalent. We demonstrate that effective charge computed by Osaka and Shindo is the Szigeti charge, and once the Born charge is computed, it is in excellent agreement with our computed value. Mulliken population analysis of Li$_{2}$O also confirms ionic nature of the bonding in the substance.Comment: 11 pages, 1 figure. To appear in Phys. Rev. B (Feb 2008

The Bravyi-Kitaev transformation for quantum computation of electronic structure

Quantum simulation is an important application of future quantum computers with applications in quantum chemistry, condensed matter, and beyond. Quantum simulation of fermionic systems presents a specific challenge. The Jordan-Wigner transformation allows for representation of a fermionic operator by O(n) qubit operations. Here we develop an alternative method of simulating fermions with qubits, first proposed by Bravyi and Kitaev [S. B. Bravyi, A.Yu. Kitaev, Annals of Physics 298, 210-226 (2002)], that reduces the simulation cost to O(log n) qubit operations for one fermionic operation. We apply this new Bravyi-Kitaev transformation to the task of simulating quantum chemical Hamiltonians, and give a detailed example for the simplest possible case of molecular hydrogen in a minimal basis. We show that the quantum circuit for simulating a single Trotter time-step of the Bravyi-Kitaev derived Hamiltonian for H2 requires fewer gate applications than the equivalent circuit derived from the Jordan-Wigner transformation. Since the scaling of the Bravyi-Kitaev method is asymptotically better than the Jordan-Wigner method, this result for molecular hydrogen in a minimal basis demonstrates the superior efficiency of the Bravyi-Kitaev method for all quantum computations of electronic structure

Antiferromagnetic Exchange Interaction between Electrons on Degenerate LUMOs in Benzene Dianion

We discuss the ground state of Benzene dianion (Bz$^{2-}$) on the basis of the numerical diagonalization method of an effective model of $\pi$ orbitals. It is found that the ground state can be the spin singlet state, and the exchange coupling between LUMOs can be antiferromagnetic.Comment: Accepted for publication in J. Phys. Soc. Jpn., 2 pages, 3 figure

A Diabatic Three-State Representation of Photoisomerization in the Green Fluorescent Protein Chromophore

We give a quantum chemical description of bridge photoisomerization reaction of green fluorescent protein (GFP) chromophores using a representation over three diabatic states. Bridge photoisomerization leads to non-radiative decay, and competes with fluorescence in these systems. In the protein, this pathway is suppressed, leading to fluorescence. Understanding the electronic structure of the photoisomerization is a prerequisite to understanding how the protein suppresses this pathway and preserves the emitting state of the chromophore. We present a solution to the state-averaged complete active space problem, which is spanned at convergence by three fragment-localized orbitals. We generate the diabatic-state representation by applying a block diagonalization transformation to the Hamiltonian calculated for the anionic chromophore model HBDI with multi-reference, multi-state perturbation theory. The diabatic states that emerge are charge-localized structures with a natural valence-bond interpretation. At planar geometries, the diabatic picture recaptures the charge transfer resonance of the anion. The strong S0-S1 excitation at these geometries is reasonably described within a two-state model, but extension to a three-state model is necessary to describe decay via two possible pathways associated with photoisomerization of the (methine) bridge. Parametric Hamiltonians based on the three-state ansatz can be fit directly to data generated using the underlying active space. We provide an illustrative example of such a parametric Hamiltonian

Closed-form expressions for correlated density matrices: application to dispersive interactions and example of (He)2

Empirically correlated density matrices of N-electron systems are investigated. Exact closed-form expressions are derived for the one- and two-electron reduced density matrices from a general pairwise correlated wave function. Approximate expressions are proposed which reflect dispersive interactions between closed-shell centro-symmetric subsystems. Said expressions clearly illustrate the consequences of second-order correlation effects on the reduced density matrices. Application is made to a simple example: the (He)2 system. Reduced density matrices are explicitly calculated, correct to second order in correlation, and compared with approximations of independent electrons and independent electron pairs. The models proposed allow for variational calculations of interaction energies and equilibrium distance as well as a clear interpretation of dispersive effects on electron distributions. Both exchange and second order correlation effects are shown to play a critical role on the quality of the results.Comment: 22 page

Weak Interactions Between Molecules

Explicit formulae are derived for the calculation of dispersion energies between large molecules, at various levels of approximmion. The derivation introduces frequency-dependent polarizabilities (FDPs), whiCh describe the propagation of electron density fluctuat-· ions within each of the separate molecules, but avoids the usual multipole expansion. The resultant dispersion energy formula reveals the presence of long-range (R-2) energy terms between moms of the different molecules and provides a basis for semi-empirical models based on pairwise atom-atom interactions. A rapidly convergent SCF procedure for calculating the required FDPs is also described