321 research outputs found
Electron correlation in C_(4N+2) carbon rings: aromatic vs. dimerized structures
The electronic structure of C_(4N+2) carbon rings exhibits competing
many-body effects of Huckel aromaticity, second-order Jahn-Teller and Peierls
instability at large sizes. This leads to possible ground state structures with
aromatic, bond angle or bond length alternated geometry. Highly accurate
quantum Monte Carlo results indicate the existence of a crossover between C_10
and C_14 from bond angle to bond length alternation. The aromatic isomer is
always a transition state. The driving mechanism is the second-order
Jahn-Teller effect which keeps the gap open at all sizes.Comment: Submitted for publication: 4 pages, 3 figures. Corrected figure
Approximate and exact nodes of fermionic wavefunctions: coordinate transformations and topologies
A study of fermion nodes for spin-polarized states of a few-electron ions and
molecules with one-particle orbitals is presented. We find exact nodes
for some cases of two electron atomic and molecular states and also the first
exact node for the three-electron atomic system in state using
appropriate coordinate maps and wavefunction symmetries. We analyze the cases
of nodes for larger number of electrons in the Hartree-Fock approximation and
for some cases we find transformations for projecting the high-dimensional node
manifolds into 3D space. The node topologies and other properties are studied
using these projections. We also propose a general coordinate transformation as
an extension of Feynman-Cohen backflow coordinates to both simplify the nodal
description and as a new variational freedom for quantum Monte Carlo trial
wavefunctions.Comment: 7 pages, 7 figure
Pfaffian pairing wave functions in electronic structure quantum Monte Carlo
We investigate the accuracy of trial wave function for quantum Monte Carlo
based on pfaffian functional form with singlet and triplet pairing. Using a set
of first row atoms and molecules we find that these wave functions provide very
consistent and systematic behavior in recovering the correlation energies on
the level of 95%. In order to get beyond this limit we explore the
possibilities of multi-pfaffian pairing wave functions. We show that a small
number of pfaffians recovers another large fraction of the missing correlation
energy comparable to the larger-scale configuration interaction wave functions.
We also find that pfaffians lead to substantial improvements in fermion nodes
when compared to Hartree-Fock wave functions.Comment: 4 pages, 2 figures, 2 tables, submitted to PR
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