Nonmechanical Conductance Switching in a Molecular Tunnel Junction

We present a molecular junction composed of a donor (polyacetylene strands) and an acceptor (malononitrile) connected together via a benzene ring and coupled weakly to source and drain electrodes on each side, for which a gate electrode induces intramolecular charge transfer, switching reversibly the character of conductance. Using a new brand of density functional theory, for which orbital energies are similar to the quasiparticle energies, we show that the junction displays a <i>single</i>, gate-tunable differential conductance channel in a wide energy range. The gate field must align parallel to the displacement vector between donors and acceptor to affect their potential difference; for strong enough fields, spontaneous intramolecular electron transfer occurs. This event radically affects conductance, reversing the charge of carriers, enabling a spin-polarized current channel. We discuss the physical principles controlling the operation of the junction and find interplay of quantum interference, charging, Coulomb blockade, and electron–hole binding energy effects. We expect that this switching behavior is a generic property for similar donor–acceptor systems of sufficient stability

Linear Weak Scalability of Density Functional Theory Calculations without Imposing Electron Localization

Linear scaling density functional theory (DFT) approaches to the electronic structure of materials are often based on the tendency of electrons to localize in large atomic and molecular systems. However, in many cases of actual interest, such as semiconductor nanocrystals, system sizes can reach a substantial extension before significant electron localization sets in, causing a considerable deviation from linear scaling. Herein, we address this class of systems by developing a massively parallel DFT approach which does not rely on electron localization and is formally quadratic scaling yet enables highly efficient linear wall-time complexity in the weak scalability regime. The method extends from the stochastic DFT approach described in Fabian et al. (WIRES: Comp. Mol. Sci. 2019, e1412) but is entirely deterministic. It uses standard quantum chemical atom-centered Gaussian basis sets to represent the electronic wave functions combined with Cartesian real-space grids for some operators and enables a fast solver for the Poisson equation. Our main conclusion is that when a processor-abundant high-performance computing (HPC) infrastructure is available, this type of approach has the potential to allow the study of large systems in regimes where quantum confinement or electron delocalization prevents linear scaling

Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theory

Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theor

Forces from Stochastic Density Functional Theory under Nonorthogonal Atom-Centered Basis Sets

We develop a formalism for calculating forces on the nuclei within the linear-scaling stochastic density functional theory (sDFT) in a nonorthogonal atom-centered basis set representation (Fabian et al. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2019, 9, e1412, 10.1002/wcms.1412) and apply it to the Tryptophan Zipper 2 (Trp-zip2) peptide solvated in water. We use an embedded-fragment approach to reduce the statistical errors (fluctuation and systematic bias), where the entire peptide is the main fragment and the remaining 425 water molecules are grouped into small fragments. We analyze the magnitude of the statistical errors in the forces and find that the systematic bias is of the order of 0.065 eV/Å (∼1.2 × 10–3Eh/a0) when 120 stochastic orbitals are used, independently of system size. This magnitude of bias is sufficiently small to ensure that the bond lengths estimated by stochastic DFT (within a Langevin molecular dynamics simulation) will deviate by less than 1% from those predicted by a deterministic calculation

Deleterious Effects of Exact Exchange Functionals on Predictions of Molecular Conductance

Kohn–Sham (KS) density functional theory (DFT) describes well the atomistic structure of molecular junctions and their coupling to the semi-infinite metallic electrodes but severely overestimates conductance due to the spuriously large density of charge-carrier states of the KS system. Previous works show that inclusion of appropriate amounts of nonlocal exchange in the functional can fix the problem and provide realistic conductance estimates. Here however we discover that nonlocal exchange can also lead to deleterious effects which artificially overestimate transmittance even beyond the KS-DFT prediction. The effect is a result of exchange coupling between nonoverlapping states of diradical character. We prescribe a practical recipe for eliminating such artifacts

Making Sense of Coulomb Explosion Imaging

A multifaceted agreement between ab initio theoretical predictions and experimental measurements, including branching ratios, channel-specific kinetic energy release, and three-body momentum correlation spectra, leads to the identification of new mechanisms in Coulomb-explosion (CE) induced two- and three-body breakup processes in methanol. These identified mechanisms include direct nonadiabatic Coulomb explosion responsible for CO bond-breaking, a long-range “ inverse harpooning” dominating the production of H2+ + HCOH+, a transient proton migration leading to surprising energy partitioning in three-body fragmentation and other complex dynamics forming products such as H2O+ and H3+. These mechanisms provide general concepts that should be useful for analyzing future time-resolved Coulomb explosion imaging of methanol as well as other molecular systems. These advances are enabled by a combination of recently developed experimental and computational techniques, using weak ultrafast EUV pulses to initiate the CE and a high-level quantum chemistry approach to follow the resulting field-free nonadiabatic molecular dynamics

Curvature and Frontier Orbital Energies in Density Functional Theory

Perdew et al. discovered two different properties of exact Kohn–Sham density functional theory (DFT): (i) The exact total energy versus particle number is a series of linear segments between integer electron points. (ii) Across an integer number of electrons, the exchange-correlation potential “jumps” by a constant, known as the derivative discontinuity (DD). Here we show analytically that in both the original and the generalized Kohn–Sham formulation of DFT the two properties are two sides of the same coin. The absence of a DD dictates deviation from piecewise linearity, but the latter, appearing as curvature, can be used to correct for the former, thereby restoring the physical meaning of orbital energies. A simple correction scheme for any semilocal and hybrid functional, even Hartree–Fock theory, is shown to be effective on a set of small molecules, suggesting a practical correction for the infamous DFT gap problem. We show that optimally tuned range-separated hybrid functionals can inherently minimize <i>both</i> DD and curvature, thus requiring no correction, and that this can be used as a sound theoretical basis for novel tuning strategies

Performance of DFT Methods in the Calculation of Optical Spectra of TCF-Chromophores

We present electronic structure calculations of the ultraviolet/visible (UV−vis) spectra of highly active push−pull chromophores containing the tricyanofuran (TCF) acceptor group. In particular, we have applied the recently developed long-range corrected Baer-Neuhauser-Livshits (BNL) exchange-correlation functional. The performance of this functional compares favorably with other density functional theory (DFT) approaches, including the CAM-B3LYP functional. The accuracy of UV−vis results for these molecules is best at low values of attenuation parameters (γ) for both BNL and CAM-B3LYP functionals. The optimal value of γ is different for the charge-transfer (CT) and π−π* excitations. The BNL and PBE0 exchange correlation functionals capture the CT states particularly well, while the π−π* excitations are less accurate and system dependent. Chromophore conformations, which considerably affect the molecular hyperpolarizability, do not significantly influence the UV−vis spectra on average. As expected, the color of chromophores is a sensitive function of modifications to its conjugated framework and is not significantly affected by increasing aliphatic chain length linking a chromophore to a polymer. For selected push−pull aryl-chromophores, we find a significant dependence of absorption spectra on the strength of diphenylaminophenyl donors

Time-Dependent Second-Order Green’s Function Theory for Neutral Excitations

We develop a time-dependent second-order Green’s function theory (GF2) for calculating neutral excited states in molecules. The equation of motion for the lesser Green’s function (GF) is derived within the adiabatic approximation to the Kadanoff–Baym (KB) equation, using the second-order Born approximation for the self-energy. In the linear response regime, we recast the time-dependent KB equation into a Bethe–Salpeter-like equation (GF2-BSE), with a kernel approximated by the second-order Coulomb self-energy. We then apply our GF2-BSE to a set of molecules and atoms and find that GF2-BSE is superior to configuration interaction with singles (CIS) and/or time-dependent Hartree–Fock (TDHF), particularly for charge-transfer excitations, and is comparable to CIS with perturbative doubles (CIS(D)) in most cases

Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

Density functional theory with optimally tuned range-separated hybrid (OT-RSH) functionals has been recently suggested [Refaely-Abramson et al. <i>Phys. Rev. Lett.</i> <b>2012</b>, <i>109</i>, 226405] as a nonempirical approach to predict the outer-valence electronic structure of molecules with the same accuracy as many-body perturbation theory. Here, we provide a quantitative evaluation of the OT-RSH approach by examining its performance in predicting the outer-valence electron spectra of several prototypical gas-phase molecules, from aromatic rings (benzene, pyridine, and pyrimidine) to more complex organic systems (terpyrimidinethiol and copper phthalocyanine). For a range up to several electronvolts away from the frontier orbital energies, we find that the outer-valence electronic structure obtained from the OT-RSH method agrees very well (typically within ∼0.1–0.2 eV) with both experimental photoemission and theoretical many-body perturbation theory data in the GW approximation. In particular, we find that with new strategies for an optimal choice of the short-range fraction of Fock exchange, the OT-RSH approach offers a balanced description of localized and delocalized states. We discuss in detail the sole exception founda high-symmetry orbital, particular to small aromatic rings, which is relatively deep inside the valence state manifold. Overall, the OT-RSH method is an accurate DFT-based method for outer-valence electronic structure prediction for such systems and is of essentially the same level of accuracy as contemporary GW approaches, at a reduced computational cost