Stability of the complex generalized Hartree-Fock equations

Goings, Joshua J.; Ding, Feizhi; Frisch, Michael J.; Xiaosong Li
April 2015
Journal of Chemical Physics;2015, Vol. 142 Issue 15, p1
Academic Journal
For molecules with complex and competing magnetic interactions, it is often the case that the lowest energy Hartree-Fock solution may only be obtained by removing the spin and time-reversal symmetry constraints of the exact non-relativistic Hamiltonian. To do so results in the complex generalized Hartree-Fock (GHF) method. However, with the loss of variational constraints comes the greater possibility of converging to higher energy minima. Here, we report the implementation of stability test of the complex GHF equations, along with an orbital update scheme should an instability be found. We apply the methodology to finding the local minima of several spin-frustrated hydrogen rings, as well as the non-collinear molecular magnet Cr3, illustrating the utility of the broken symmetry GHF method and some of its lesser-known nuances.


Related Articles

  • The katoite hydrogarnet Si-free Ca3Al2([OH]4)3: A periodic Hartree–Fock and B3-LYP study. Pascale, F.; Ugliengo, P.; Civalleri, B.; Orlando, R.; D'Arco, P.; Dovesi, R. // Journal of Chemical Physics;7/8/2004, Vol. 121 Issue 2, p1005 

    The structure of the Si-free katoite hydrogarnet (116 atoms in the unit cell) has been investigated at the periodic ab initio quantum mechanical level with the CRYSTAL program, by using a Gaussian type basis set and both the HF and the hybrid B3-LYP Hamiltonians. The structure has been fully...

  • Magnetic properties of Hubbard clusters; Noncollinear spins in N-atom clusters. Ojeda-Lopez, M.A.; Dorantes-Davila, J. // Journal of Applied Physics;4/16/1997, Vol. 81 Issue 8, p4170 

    Studies the ground-state magnetic properties of clusters with N-atomic sites by solving the single-band Hubbard Hamiltonian in the unrestricted Hartree-Fock approximation. Consideration of three-dimensional arrangements of spins; Results for stability and magnetic order as a function of the...

  • A multireference perturbation method using non-orthogonal Hartree-Fock determinants for ground and excited states. Yost, Shane R.; Kowalczyk, Tim; Van Voorhis, Troy // Journal of Chemical Physics;Nov2013, Vol. 139 Issue 17, p174104 

    In this article we propose the ΔSCF(2) framework, a multireference strategy based on second-order perturbation theory, for ground and excited electronic states. Unlike the complete active space family of methods, ΔSCF(2) employs a set of self-consistent Hartree-Fock determinants, also...

  • Structure and vibrations of phenol(H2O)2. Gerhards, M.; Kleinermanns, K. // Journal of Chemical Physics;11/1/1995, Vol. 103 Issue 17, p7392 

    Extensive ab initio calculations at the Hartree–Fock (HF) level using different basis sets have been performed in order to obtain the minimum energy structure of the phenol(H2O)2-cluster. Several hydrogen bonding arrangements and a van der Waals structure are discussed. The most stable...

  • A quantitative study of the scaling properties of the Hartree–Fock method. Strout, Douglas L.; Scuseria, Gustavo E. // Journal of Chemical Physics;6/1/1995, Vol. 102 Issue 21, p8448 

    Although it is usually stated that the Hartree–Fock method formally scales as N4, where N is the number of basis functions employed in the calculation, it is also well known that mathematical bounds computed with the Schwarz inequality can be used to screen and eliminate four-center...

  • Periodic Hartree–Fock calculations on crystalline HCN. Platts, J. A.; Howard, S. T. // Journal of Chemical Physics;9/15/1996, Vol. 105 Issue 11, p4668 

    Periodic Hartree–Fock calculations on the tetragonal, high temperature, form of solid HCN are presented. Using HF/6-31G** methodology, the lattice energy per molecule is predicted to be 21.8 kJ mol-1, in good agreement with an experimental value of 19 kJ mol-1. Atoms-in-molecules...

  • The basis set convergence of the Hartree-Fock energy for H[sub 2]. Jensen, Frank // Journal of Chemical Physics;4/8/1999, Vol. 110 Issue 14, p6601 

    Illustrates that the Hartree-Fock energy approximation for the hydrogen2 molecule converges exponentially. Influence of the number of basis functions on a given type; Factors that determine the subnanohartree accuracy.

  • Basis set convergence of the interaction energy of hydrogen-bonded complexes. Halkier, Asger; Klopper, Wim // Journal of Chemical Physics;11/22/1999, Vol. 111 Issue 20, p9157 

    Computes the Hartree-Fock approximation and correlation contributions to the interaction energy of hydrogen-bonded complexes in conventional calculations employing the aug-cc-pVXZ series of basis sets. Examination of the basis set convergence of the interaction energy; Findings indicating that...

  • Hartree–Fock–Slater-LCAO implementation of the moderately large-embedded-cluster approach to chemisorption. Calculations for hydrogen on lithium (100). Ravenek, Walter; Geurts, Ferdie M. M. // Journal of Chemical Physics;2/1/1986, Vol. 84 Issue 3, p1613 

    We discuss the implementation of Pisani’s moderately large-embedded-cluster scheme in the pseudopotential version of the Hartree–Fock–Slater-LCAO method. We confine ourselves to the chemisorption problem and use a finite representation for the substrate. As an illustration...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics