Open-system Kohn-Sham density functional theory

Zhou, Yongxi; Ernzerhof, Matthias

doi:10.1063/1.3687922

Cited by 17 publications

(36 citation statements)

References 45 publications

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“…Dissociative recombination via autoionizing states is important in interstellar chemistry (4). Resonances are also involved in condensed-phase processes, e.g., in radiolysis and damage to DNA by slow electrons (5,6), single-molecule electronics (7), and plasmonic catalysis (8,9) (see the sidebar titled Plasmonic Catalysis).…”

Section: Introduction: What Is a Resonance?mentioning

confidence: 99%

Extending Quantum Chemistry of Bound States to Electronic Resonances

Jagau

Bravaya

Krylov

2017

Annu. Rev. Phys. Chem.

167

263

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Electronic resonances are metastable states with finite lifetime embedded in the ionization or detachment continuum. They are ubiquitous in chemistry, physics, and biology. Resonances play a central role in processes as diverse as DNA radiolysis, plasmonic catalysis, and attosecond spectroscopy. This review describes novel equation-of-motion coupled-cluster (EOM-CC) methods designed to treat resonances and bound states on an equal footing. Built on complex-variable techniques such as complex scaling and complex absorbing potentials that allow resonances to be associated with a single eigenstate of the molecular Hamiltonian rather than several continuum eigenstates, these methods extend electronic-structure tools developed for bound states to electronic resonances. Selected examples emphasize the formal advantages as well as the numerical accuracy of EOM-CC in the treatment of electronic resonances. Connections to experimental observables such as spectra and cross sections, as well as practical aspects of implementing complex-valued approaches, are also discussed.

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Section: Introduction: What Is a Resonance?mentioning

confidence: 99%

Extending Quantum Chemistry of Bound States to Electronic Resonances

Jagau

Bravaya

Krylov

2017

Annu. Rev. Phys. Chem.

167

263

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“…[35][36][37][38] The method of source-sink potentials is a second example where the Hamiltonian of the finite system is augmented by source and sink terms that serve to inject and absorb electrons near the physical boundaries of the finite system. [39][40][41][42][43] One of the earliest time-dependent approaches developed along these lines suggested that the explicit calculation of leads' self-energies can be avoided by approximating them with complex absorbing potentials. [44][45][46] Here, the timedependent response of the finite system to an external electric field perturbation 44,45 or local edge potentials 46 is simulated and the excited electrons are absorbed near the boundaries, thus dissipating the excess energy that they carry and avoiding back-scattering into the system.…”

Section: Introductionmentioning

confidence: 99%

State Representation Approach for Atomistic Time-Dependent Transport Calculations in Molecular Junctions

Zelovich

Kronik

Hod

2014

J. Chem. Theory Comput.

162

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Abstract:We propose a new method for simulating electron dynamics in open quantum systems out of equilibrium, using a finite atomistic model. The proposed method is motivated by the intuitive and practical nature of the driven Liouville vonNeumann equation approach of Sánchez et al. [J. Chem. Phys., 124, 214708 (2006)]. A key ingredient of our approach is a transformation of the Hamiltonian matrix from an atomistic to a state representation of the molecular junction. This allows us to uniquely define the bias voltage across the system while maintaining a proper thermal electronic distribution within the finite lead models. Furthermore, it allows us to investigate complex molecular junctions, including non-linear setups and multi-lead configurations. A heuristic derivation of our working equation leads to explicit expressions for the damping and driving terms, which serve as appropriate electron sources and sinks that effectively "open" the finite model system.Although the method does not forbid it, in practice we find neither violation of Pauli's exclusion principles nor deviation from density matrix positivity throughout our numerical simulations of various tight-binding model systems. We believe that the new approach offers a practical and physically sound route for performing atomistic time-dependent transport calculations in realistic molecular junctions.2

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“…Until recently, 18 the SSP method had only been implemented for Hückel models 14,19,20,21,22 This is because the determinantal equation reduces to an n L × n L determinant for such models; n L is the number of open channels on the left, the source of the incoming wave. For incoming waves on the right, the determinant is n R × n R .…”

Section: The Source-sink Potential Methodsmentioning

confidence: 99%

“…The zeroth-order reference system is the isolated neutral molecule for which the atomic charge distribution is given by (18) …”

Section: Model Of Molecular Charging and Polarization Accompanying Nomentioning

confidence: 99%

Effects of charging and polarization on molecular conduction via the source-sink potential method

Dumont

2014

Can. J. Chem.

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The current−voltage relationships of butadiene and octatetraene are computed using the source-sink potential method with self-consistent Hückel theory. Molecular orbital resonances appear as steps in current, considerably broader than the resonances in the transmission spectrum at any specific bias. This broadening is due primarily to the charging of the molecule as bias increases. A perturbation theory based model is derived to account for the observations. In the case of octatetraene, the HOMO resonance manifests at high voltage when the HOMO energy is raised to the Fermi level of the plus electrode due to the charging of the LUMO and LUMO + 1 levels. Specifically, the LUMO and LUMO + 1 steps in current are augmented by portions of the HOMO contribution to current. Résumé :On fait appel à la méthode des potentiels source-puits et à la théorie de Hückel auto-cohérente pour calculer les relations intensité−tension du butadiène et de l'octatétraène. Les résonances avec les orbitales moléculaires apparaissent comme des sauts d'intensité considérablement plus larges que les résonances dans le spectre de transmission à tout biais particulier. Cet élargissement est principalement attribuable au chargement de la molécule à mesure que le biais augmente. On dérive un modèle basé sur la théorie des perturbations pour expliquer les observations. Dans le cas de l'octatétraène, la résonance avec la HOMO se manifeste à une tension élevée quand l'énergie de la HOMO augmente pour atteindre le niveau de Fermi de l'électrode positive en raison du chargement des niveaux LUMO et LUMO + 1. En particulier, les sauts d'intensité aux niveaux LUMO et LUMO + 1 sont accrus par des portions de la contribution de la HOMO à l'intensité. [Traduit par la Rédaction]

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Open-system Kohn-Sham density functional theory

Cited by 17 publications

References 45 publications

Extending Quantum Chemistry of Bound States to Electronic Resonances

Extending Quantum Chemistry of Bound States to Electronic Resonances

State Representation Approach for Atomistic Time-Dependent Transport Calculations in Molecular Junctions

Effects of charging and polarization on molecular conduction via the source-sink potential method

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