303 research outputs found
Analytic Energy Gradients for Multiconfigurational Self-Consistent Field Second-Order Quasidegenerate Perturbation Theory (MC-QDPT)
An analytic energy gradient method for second-order quasidegenerate perturbation theory with multiconfigurational self-consistent field reference functions (MC-QDPT) is derived along the lines of the response function formalism (RFF). According to the RFF, the gradients are calculated without solving coupled perturbed equations. Instead, it is necessary to solve seven sets of linear equations in order to determine Lagrangian multipliers, corresponding to four sets of parameter constraining conditions and three sets of additional parameter defining conditions in the Lagrangian. Just one of these linear equations is a large scale linear equation; the others are reducible to just partial differentiations or simple equations solvable by straightforward subroutines
Interaction and Localization of One-electron Orbitals in an Organic Molecule: Fictitious Parameter Analysis for Multi-physics Simulations
We present a new methodology to analyze complicated multi-physics simulations
by introducing a fictitious parameter. Using the method, we study quantum
mechanical aspects of an organic molecule in water. The simulation is
variationally constructed from the ab initio molecular orbital method and the
classical statistical mechanics with the fictitious parameter representing the
coupling strength between solute and solvent. We obtain a number of
one-electron orbital energies of the solute molecule derived from the
Hartree-Fock approximation, and eigenvalue-statistical analysis developed in
the study of nonintegrable systems is applied to them. Based on the results, we
analyze localization properties of the electronic wavefunctions under the
influence of the solvent.Comment: 4 pages, 5 figures, the revised version will appear in J. Phys. Soc.
Jpn. Vol.76 (No.1
Designing all-graphene nanojunctions by covalent functionalization
We investigated theoretically the effect of covalent edge functionalization,
with organic functional groups, on the electronic properties of graphene
nanostructures and nano-junctions. Our analysis shows that functionalization
can be designed to tune electron affinities and ionization potentials of
graphene flakes, and to control the energy alignment of frontier orbitals in
nanometer-wide graphene junctions. The stability of the proposed mechanism is
discussed with respect to the functional groups, their number as well as the
width of graphene nanostructures. The results of our work indicate that
different level alignments can be obtained and engineered in order to realize
stable all-graphene nanodevices
A mathematical and computational review of Hartree-Fock SCF methods in Quantum Chemistry
We present here a review of the fundamental topics of Hartree-Fock theory in
Quantum Chemistry. From the molecular Hamiltonian, using and discussing the
Born-Oppenheimer approximation, we arrive to the Hartree and Hartree-Fock
equations for the electronic problem. Special emphasis is placed in the most
relevant mathematical aspects of the theoretical derivation of the final
equations, as well as in the results regarding the existence and uniqueness of
their solutions. All Hartree-Fock versions with different spin restrictions are
systematically extracted from the general case, thus providing a unifying
framework. Then, the discretization of the one-electron orbitals space is
reviewed and the Roothaan-Hall formalism introduced. This leads to a exposition
of the basic underlying concepts related to the construction and selection of
Gaussian basis sets, focusing in algorithmic efficiency issues. Finally, we
close the review with a section in which the most relevant modern developments
(specially those related to the design of linear-scaling methods) are commented
and linked to the issues discussed. The whole work is intentionally
introductory and rather self-contained, so that it may be useful for non
experts that aim to use quantum chemical methods in interdisciplinary
applications. Moreover, much material that is found scattered in the literature
has been put together here to facilitate comprehension and to serve as a handy
reference.Comment: 64 pages, 3 figures, tMPH2e.cls style file, doublesp, mathbbol and
subeqn package
Use of Combined Hartree-Fock-Roothaan Theory in Evaluation of Lowest States of K [Ar]4s^0 3d^1 and Cr+ [Ar]4s^0 3d^5 Isoelectronic Series Over Noninteger n-Slater Type Orbitals
By the use of integer and noninteger n-Slater Type Orbitals in combined
Hartree-Fock-Roothaan method, self consistent field calculations of orbital and
lowest states energies have been performed for the isoelectronic series of open
shell systems K [Ar]4s^0 3d^1 2(D) (Z=19-30) and Cr+ [Ar] 4s^0 3d^5 6(S)
(Z=24-30). The results of calculations for the orbital and total energies
obtained from the use of minimal basis sets of integer- and noninteger n-Slater
Type Orbitals are given in tables. The results are compared with the
extended-basis Hartree-Fock computations. The orbital and total energies are in
good agreement with those presented in the literature. The results are
accurately and considerably can be useful in the application of
non-relativistic and relativistic combined Hartree-Fock-Roothaan approach for
heavy atomic systems.Comment: 11 pages, 6 tables, 2 figures. submitte
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