Parallelization of four‐component calculations. I. Integral generation,SCF, and four‐index transformation in the Dirac–Fock package MOLFDIR

The treatment of relativity and electron correlation on an equal footing is essential for the computation of systems containing heavy elements. Correlation treatments that are based on four‐component Dirac–Hartree–Fock calculations presently provide the most accurate, albeit costly, way of taking relativity into account. The requirement of having two expansion basis sets for the molecular wave function puts a high demand on computer resources. The treatment of larger systems is thereby often prohibited by the very large run times and files that arise in a conventional Dirac–Hartree–Fock approach. A possible solution for this bottleneck is a parallel approach that not only reduces the turnaround time but also spreads out the large files over a number of local disks. Here, we present a distributed‐memory parallelization of the program package MOLFDIR for the integral generation, Dirac–Hartree–Fock and four‐index MS transformation steps. This implementation scales best for large AO spaces and moderately sized active spaces. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1176–1186, 2000     

Ab initio conformational analysis of cyclooctane molecule

The potential energy surface (PES) for the cyclooctane molecule was comprehensively investigated at the Hartree–Fock (HF) level of theory employing the 3–21G, 6–31G, and 6–31G* basis sets. Six distinct true minimum energy structures (named B, BB, BC, CROWN, TBC, and TCC₁), characterized through harmonic frequency analysis, were located on the multidimensional PES. Two transition state structures were also located on the PES for the cyclooctane molecule. Electron correlation effects were accounted for using the Møller–Plesset second-order perturbation theory (MP2) approach. The predicted global minimum energy structure on the ab initio PES for the cyclooctane molecule is the BC conformer. A gas phase electron diffraction study at 300 K suggested a conformational mixture while an NMR study in solution at 161.5 K predicted the BC conformer as the predominant form. The equilibrium constants reported in the present study, which were evaluated from the ab initio calculated total Gibbs free energy change values, were in good agreement with both experimental investigations. The ab initio results showed that the low temperature condition significantly favored the BC conformer while above room temperature both BC and CROWN structures can coexist. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 524–534, 1998     

Self-consistent field calculations using two-body density functionals for correlation energy component: I. Atomic systems

Self-consistent field calculations are done using two-body density functionals for the correlation energy. The corresponding functional derivatives are obtained and used in pseudo-eigenvalue equations analogous to the Kohn–Sham ones. The examples studied include atomic systems from He to Ar. The values obtained for ionization potentials, electron affinities, dipole polarizabilities, and virial ratios from these calculations are given, and the effect of exchange is addressed. The results obtained are in good agreement with experimental values, and are of the same quality as those given by accurate exchange-correlation functionals. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1887–1898, 1998     

Parallel pseudospectral electronic structure: I. Hartree–Fock calculations

We present an outline of the parallel implementation of our pseudospectral electronic structure program, Jaguar, including the algorithm and timings for the Hartree–Fock and analytic gradient portions of the program. We also present the parallel algorithm and timings for our Lanczos eigenvector refinement code and demonstrate that its performance is superior to the ScaLAPACK diagonalization routines. The overall efficiency of our code increases as the size of the calculation is increased, demonstrating actual as well as theoretical scalability. For our largest test system, alanine pentapeptide [818 basis functions in the cc-pVTZ(-f) basis set], our Fock matrix assembly procedure has an efficiency of nearly 90% on a 16-processor SP2 partition. The SCF portion for this case (including eigenvector refinement) has an overall efficiency of 87% on a partition of 8 processors and 74% on a partition of 16 processors. Finally, our parallel gradient calculations have a parallel efficiency of 84% on 8 processors for porphine (430 basis functions). © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1017–1029, 1998     

Theoretical study of 1,3-dipolar cycloadditions of nitrone and fulminic acid with substituted ethylenes

Molecular orbital calculations were performed to examine the electronic effects involved in the regioselectivity in the 1,3-dipolar cycloaddition reaction of nitrone and fulminic acid. The substituted ethylene dipolarophiles were selected to represent a range of electron-donating/withdrawing abilities: amino, methyl, carbaldehyde (both in the s-cis and the s-trans conformations), and nitrile. The reactions were all asynchronous, with early transition sites. The regioselectivity was correlated with the ability of the substituent to donate or withdraw electrons. With electron-donating substituents, the substituent was directed preferentially to the oxygen end of the dipole and this shifted toward the other regioisomer as the electron-withdrawing ability of the substitutent increased. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1795–1804, 1998     

Can we outperform the DIIS approach for electronic structure calculations?

This article regroups various results on self-consistent field algorithms for computing electronic structures of molecular systems. The first part deals with the convergence properties of the “conventional” Roothaan algorithm and of the level-shifting algorithm. In the second part, a new class of algorithms is introduced, for which convergence is guaranteed by mathematical arguments. Computational performance on various test problems is reported; advantages of this new approach are demonstrated. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 82–90, 2000     

极化自由度对分束器出射光场的量子相干性影响的研究

我们在讨论粒子数态光场在分束器上干涉后得到的输出态的量子相干性时,考虑了入射场的极化自由度.利用campos[1]等人提出的量子分束器的SU(2)理论模型,计算得到了输出光场所处状态的表达式.进而讨论了光场在两个不同的入射空间模上极化方向对两个输出空间模上光场二阶量子干涉度的影响.     

Truncation of small matrix elements based on the Euclidean norm for blocked data structures

Methods for the removal of small symmetric matrix elements based on the Euclidean norm of the error matrix are presented in this article. In large scale Hartree-Fock and Kohn-Sham calculations it is important to be able to enforce matrix sparsity while keeping errors under control. Truncation based on some unitary-invariant norm allows for control of errors in the occupied subspace as described in (Rubensson et al. J Math Phys 49, 032103). The Euclidean norm is unitary-invariant and does not grow intrinsically with system size and is thus suitable for error control in large scale calculations. The presented truncation schemes repetitively use the Lanczos method to compute the Euclidean norms of the error matrix candidates. Ritz value convergence patterns are utilized to reduce the total number of Lanczos iterations.     

Quantum chemical investigation of lanthanum doping effects in tetragonal and rhombohedral PZT materials

Structural and electronic properties of lead–zirconate–titanate (PZT) materials doped with a lanthanum (La) impurity are studied using a quantum‐chemical approach based on the Hartree–Fock theory. Performed geometry optimization in the defective crystals shows that the atomic movements are predominantly outward with respect to the impurity position. It is found that the La impurity enhances a covalent character in the chemical bonding between the Ti and O atoms, as well as the Zr and O atoms situated in the neighborhood of the defect despite the fact that the La‐O interaction remains purely ionic. The occurrence of local energy levels within the band gap of the material is analyzed in light of the available experimental data on La concentration influence upon dielectric and piezoelectric properties in these crystals. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009