Performance of the Harris functional for extended basis sets at the Hartree-Fock and density functional levels

The Harris functional is a noniterative variational procedure that uses an input charge density to produce an energy that is surprisingly accurate compared to the converged Kohn-Sham self-consistent result. We adapted and generalized this functional for the Hartree-Fock closed- and open-shell cases as well as examined its use for hybrid density functional methods such as B3LYP. Analysis of extended basis set calculations shows that at the B3LYP level an input density formed from a double zeta + polarization orbital basis is accurate enough to reproduce the energy of triple zeta + double polarization + diffuse orbital basis. For large molecules this translates into a computational speed that can be an order of magnitude faster. In the case of Hartree-Fock calculations a "bootstrapping technique" that employs successive applications of the Harris functional can further reduce computational times while retaining sufficient accuracy.     

A hierarchic sparse matrix data structure for large-scale Hartree-Fock/Kohn-Sham calculations

A hierarchic sparse matrix data structure for Hartree-Fock/Kohn-Sham calculations is presented. The data structure makes the implementation of matrix manipulations needed for large systems faster, easier, and more maintainable without loss of performance. Algorithms for symmetric matrix square and inverse Cholesky decomposition within the hierarchic framework are also described. The presented data structure is general; in addition to its use in Hartree-Fock/Kohn-Sham calculations, it may also be used in other research areas where matrices with similar properties are encountered. The applicability of the data structure to ab initio calculations is shown with help of benchmarks on water droplets and graphene nanoribbons.     

Implementation of divide-and-conquer method including Hartree-Fock exchange interaction

The divide-and-conquer (DC) method, which is one of the linear-scaling methods avoiding explicit diagonalization of the Fock matrix, has been applied mainly to pure density functional theory (DFT) or semiempirical molecular orbital calculations so far. The present study applies the DC method to such calculations including the Hartree-Fock (HF) exchange terms as the HF and hybrid HF/DFT. Reliability of the DC-HF and DC-hybrid HF/DFT is found to be strongly dependent on the cut-off radius, which defines the localization region in the DC formalism. This dependence on the cut-off radius is assessed from various points of view: that is, total energy, energy components, local energies, and density of states. Additionally, to accelerate the self-consistent field convergence in DC calculations, a new convergence technique is proposed.     

Entangling Lattice-Trapped Bosons with a Free Impurity: Impact on Stationary and Dynamical Properties

We address the interplay of few lattice trapped bosons interacting with an impurity atom in a box potential. For the ground state, a classification is performed based on the fidelity allowing to quantify the susceptibility of the composite system to structural changes due to the intercomponent coupling. We analyze the overall response at the many-body level and contrast it to the single-particle level. By inspecting different entropy measures we capture the degree of entanglement and intraspecies correlations for a wide range of intra- and intercomponent interactions and lattice depths. We also spatially resolve the imprint of the entanglement on the one- and two-body density distributions showcasing that it accelerates the phase separation process or acts against spatial localization for repulsive and attractive intercomponent interactions, respectively. The many-body effects on the tunneling dynamics of the individual components, resulting from their counterflow, are also discussed. The tunneling period of the impurity is very sensitive to the value of the impurity-medium coupling due to its effective dressing by the few-body medium. Our work provides implications for engineering localized structures in correlated impurity settings using species selective optical potentials.     

On the global Cauchy problem for the Hartree equation with rapidly decaying initial data

This paper is concerned with the Cauchy problem for the Hartree equation on ${\mathbb{R}}^n,n\in \mathbb{N}$ with the nonlinearity of type $(|?{|}^{?\gamma }?|u{|}^2)u,0<\gamma <n$. It is shown that a global solution with some twisted persistence property exists for data in the space $L^p\cap L^2,1\le p\le 2$ under some suitable conditions on γ and spatial dimension $n\in \mathbb{N}$. It is also shown that the global solution u has a smoothing effect in terms of spatial integrability in the sense that the map $t?u(t)$ is well defined and continuous from $\mathbb{R}?\{0\}$ to $L^{p^{\prime }}$, which is well known for the solution to the corresponding linear Schrödinger equation. Local and global well-posedness results for hat $L^p$-spaces are also presented. The local and global results are proved by combining arguments by Carles–Mouzaoui with a new functional framework introduced by Zhou. Furthermore, it is also shown that the global results can be improved via generalized dispersive estimates in the case of one space dimension.     

Hyper Raman spectra calculated in a time-dependent Hartree–Fock method

Hyper Raman scattering (HRS) of the benzonitrile (BN) and 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) molecules is studied by means of ab initio calculations. The computational procedure employs a recently developed methodology for the analytic calculations of frequency-dependent polarizability gradients of arbitrary order, including perturbation dependent basis sets. The result are compared to normal Raman scattering (NRS) and coherent anti-Stokes Raman scattering (CARS) that previously have been studied using the same technology. It is found that some suppressed or silent modes in CARS and NRS spectra are clearly seen in HRS, and that although under general excitation conditions the HRS intensities are much lower than for CARS and NRS, HRS provides complementary information useful for target identification.     

FT‐IR,FT‐Raman and SERS spectra of anilinium sulfate

The FT‐IR and FT‐Raman spectra of anilinium sulfate were recorded and analyzed. The surface‐enhanced Raman scattering (SERS) was recorded from a silver electrode. The vibrational wavenumbers of the compound have been computed using the Hartree‐Fock/6‐31G* basis and compared with the experimental values. The molecule is adsorbed on the silver surface with the benzene ring in a tilted orientation. The presence of amino and sulfate group vibrations in the SERS spectrum reveal the interaction between amino and sulfate groups with the silver surface. The direction of the charge transfer contribution to SERS has been discussed from the frontier orbital theory. Copyright © 2009 John Wiley & Sons, Ltd.     

临界Hartree方程组基态解的存在性

本文考虑临界耦合的Hartree方程组{-△+λu=∫Ω|u(z)|^2*μ/|x-z|μdz|u|^2*μ-2u+βν,x∈Ω,-△+νu=∫Ω|ν(z)|^2*μ/|x-z|μdz|u|^2*μ-2u+βν,x∈Ω,其中Ω是RN中带有光滑边界的有界区域,N≥3,λ,v是常数,且满足λ,v>-λ1(Ω),λ1(Ω)是(-△,H01(Ω))的第一特征值,β> 0是耦合参数,临界指标2μ*=(2N-μ)/(N-2)来源于Hardy-LittlewoodSobolev不等式,利用变分的方法证明了临界Hartree方程组基态正解的存在性.