12,721 research outputs found
Exchange-energy functionals for finite two-dimensional systems
Implicit and explicit density functionals for the exchange energy in finite
two-dimensional systems are developed following the approach of Becke and
Roussel [Phys. Rev. A 39, 3761 (1989)]. Excellent agreement for the
exchange-hole potentials and exchange energies is found when compared with the
exact-exchange reference data for the two-dimensional uniform electron gas and
few-electron quantum dots, respectively. Thereby, this work significantly
improves the availability of approximate density functionals for dealing with
electrons in quasi-two-dimensional structures, which have various applications
in semiconductor nanotechnology.Comment: 5 pages, 3 figure
Implicit and explicit host effects on excitons in pentacene derivatives
An ab initio study of the effects of implicit and explicit hosts on the excited state properties of pentacene and its nitrogen-based derivatives has been performed using ground state density func- tional theory (DFT), time-dependent DFT and ∆SCF. We observe a significant solvatochromic redshift in the excitation energy of the lowest singlet state (S 1 ) of pentacene from inclusion in a p -terphenyl host compared to vacuum; for an explicit host consisting of six nearest neighbour p -terphenyls, we obtain a redshift of 65 meV while a conductor-like polarisable continuum model (CPCM) yields a 78 meV redshift. Comparison is made between the excitonic properties of pen- tacene and four of its nitrogen-based analogues, 1,8-, 2,9-, 5,12-, and 6,13-diazapentacene with the latter found to be the most distinct due to local distortions in the ground state electronic struc- ture. We observe that a CPCM is insufficient to fully understand the impact of the host due to the presence of a mild charge-transfer (CT) coupling between the chromophore and neighbouring p -terphenyls, a phenomenon which can only be captured using an explicit model. The strength of this CT interaction increases as the nitrogens are brought closer to the central acene ring of pentacene
Electrostatic considerations affecting the calculated HOMO-LUMO gap in protein molecules.
A detailed study of energy differences between the highest occupied and
lowest unoccupied molecular orbitals (HOMO-LUMO gaps) in protein systems and
water clusters is presented. Recent work questioning the applicability of
Kohn-Sham density-functional theory to proteins and large water clusters (E.
Rudberg, J. Phys.: Condens. Mat. 2012, 24, 072202) has demonstrated vanishing
HOMO-LUMO gaps for these systems, which is generally attributed to the
treatment of exchange in the functional used. The present work shows that the
vanishing gap is, in fact, an electrostatic artefact of the method used to
prepare the system. Practical solutions for ensuring the gap is maintained when
the system size is increased are demonstrated. This work has important
implications for the use of large-scale density-functional theory in
biomolecular systems, particularly in the simulation of photoemission, optical
absorption and electronic transport, all of which depend critically on
differences between energies of molecular orbitals.Comment: 13 pages, 4 figure
Ions in solution: Density Corrected Density Functional Theory (DC-DFT)
Standard density functional approximations often give questionable results
for odd-electron radical complexes, with the error typically attributed to
self-interaction. In density corrected density functional theory (DC-DFT),
certain classes of density functional theory calculations are significantly
improved by using densities more accurate than the self-consistent densities.
We discuss how to identify such cases, and how DC-DFT applies more generally.
To illustrate, we calculate potential energy surfaces of HOCl and
HOHO complexes using various common approximate functionals, with
and without this density correction. Commonly used approximations yield wrongly
shaped surfaces and/or incorrect minima when calculated self consistently,
while yielding almost identical shapes and minima when density corrected. This
improvement is retained even in the presence of implicit solvent
Joint Density-Functional Theory of the Electrode-Electrolyte Interface: Application to Fixed Electrode Potentials, Interfacial Capacitances, and Potentials of Zero Charge
This work explores the use of joint density-functional theory, a new form of
density-functional theory for the ab initio description of electronic systems
in thermodynamic equilibrium with a liquid environment, to describe
electrochemical systems. After reviewing the physics of the underlying
fundamental electrochemical concepts, we identify the mapping between commonly
measured electrochemical observables and microscopically computable quantities
within an, in principle, exact theoretical framework. We then introduce a
simple, computationally efficient approximate functional which we find to be
quite successful in capturing a priori basic electrochemical phenomena,
including the capacitive Stern and diffusive Gouy-Chapman regions in the
electrochemical double layer, quantitative values for interfacial capacitance,
and electrochemical potentials of zero charge for a series of metals. We
explore surface charging with applied potential and are able to place our ab
initio results directly on the scale associated with the Standard Hydrogen
Electrode (SHE). Finally, we provide explicit details for implementation within
standard density-functional theory software packages at negligible
computational cost over standard calculations carried out within vacuum
environments.Comment: 18 pages, 5 figures. Initially presented at APS March Meeting 2010.
Accepted for publication in Physical Review B on Jul. 27, 201
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