Fundamental gap renormalization due to electronic polarization is a basic phenomenon in molecular crystals. Despite its ubiquity and importance, all conventional approaches within density-functional theory completely fail to capture it, even qualitatively. Here, we present a new screened range-separated hybrid functional, which, through judicious introduction of the scalar dielectric constant, quantitatively captures polarization-induced gap renormalization, as demonstrated on the prototypical organic molecular crystals of benzene, pentacene, and C60. This functional is predictive, as it contains system-specific adjustable parameters that are determined from first principles, rather than from empirical considerations.

A recently introduced molecular junction, for which the gate acts as an on/off switch for intrajunction electron transfer between localized donor and acceptor sites is studied. We demonstrate that a Landauer + density functional (DFT) approach is fundamentally flawed for describing the electronic conductance in this system. By comparing the Landauer + DFT conductance to that predicted by the Redfield quantum master equations, we point out several effects that cannot be explained by the former approach. The molecular junction is unique in the small number of conductance channels and their sharp response to the gate.

We develop an alternative formulation in the energy-domain to calculate the second order Møller–Plesset (MP2) perturbation energies. The approach is based on repeatedly choosing four random energies using a nonseparable guiding function, filtering four random orbitals at these energies, and averaging the resulting Coulomb matrix elements to obtain a statistical estimate of the MP2 correlation energy. In contrast to our time-domain formulation, the present approach is useful for both quantum chemistry and real-space/plane wave basis sets. The scaling of the MP2 calculation is roughly linear with system size, providing a useful tool to study dispersion energies in large systems. This is demonstrated on a structure of 64 fullerenes within the SZ basis as well as on silicon nanocrystals using real-space grids.

We study how shape affects multiexciton generation rates in a semiconducting nanocrystal by considering CdSe nanorods with varying diameters and aspect ratios. The calculations employ an atomistic semiempirical pseudopotential model combined with an efficacious stochastic approach applied to systems containing up to 20 000 atoms. The effect of nanorod diameter and aspect ratio on multiexciton generation rates is analyzed in terms of the scaling of the density of trion states and the scaling of the Coulomb couplings. Both show distinct scaling from spherical nanocrystals leading to a surprising result where the multiexciton generation rates are roughly independent of the nanorod length.

We formulate the Kohn-Sham density functional theory (KS-DFT) as a statistical theory in which the electron density is determined from an average of correlated stochastic densities in a trace formula. The key idea is that it is sufficient to converge the total energy per electron to within a predefined statistical error in order to obtain reliable estimates of the electronic band structure, the forces on nuclei, the density and its moments, etc. The fluctuations in the total energy per electron are guaranteed to decay to zero as the system size increases. This facilitates “self-averaging” which leads to the first ever report of sublinear scaling KS-DFT electronic structure. The approach sidesteps calculation of the density matrix and thus, is insensitive to its evasive sparseness, as demonstrated here for silicon nanocrystals. The formalism is not only appealing in terms of its promise to far push the limits of application of KS-DFT, but also represents a cognitive change in the way we think of electronic structure calculations as this stochastic theory seamlessly converges to the thermodynamic limit.

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 both DD and curvature, thus requiring no correction, and that this can be used as a sound theoretical basis for novel tuning strategies.

The range-separated Baer-Neuhauser-Livshits functional with optimized range-separation parameter \gamma was employed to predict ionization energies of alkanes and oligothiophenes. For all systems negative orbital energies of neutral species are consistent with explicitly calculated states of cations. For \sigma-systems excellent agreement with experiment is obtained while for conjugated π-systems IPs are underestimated.

We present a method for obtaining outer-valence quasiparticle excitation energies from a density-functional-theory-based calculation, with an accuracy that is comparable to that of many-body perturbation theory within the GW approximation. The approach uses a range-separated hybrid density functional, with an asymptotically exact and short-range fractional Fock exchange. The functional contains two parameters, the range separation and the short-range Fock fraction. Both are determined nonempirically, per system, on the basis of the satisfaction of exact physical constraints for the ionization potential and frontier-orbital many-electron self-interaction, respectively. The accuracy of the method is demonstrated on four important benchmark organic molecules: perylene, pentacene, 3,4,9,10-perylene-tetracarboxylic-dianydride (PTCDA), and 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA). We envision that for the outer-valence excitation spectra of finite systems the approach could provide an inexpensive alternative to GW, opening the door to the study of presently out of reach large-scale systems.

Excitation gaps are of considerable significance in electronic structure theory. Two different gaps are of particular interest. The fundamental gap is defined by charged excitations, as the difference between the first ionization potential and the first electron affinity. The optical gap is defined by a neutral excitation, as the difference between the energies of the lowest dipole-allowed excited state and the ground state. Within many-body perturbation theory, the fundamental gap is the difference between the corresponding lowest quasi-hole and quasi-electron excitation energies, and the optical gap is addressed by including the interaction between a quasi-electron and a quasi-hole. A long-standing challenge has been the attainment of a similar description within density functional theory (DFT), with much debate on whether this is an achievable goal even in principle. Recently, we have constructed and applied a new approach to this problem. Anchored in the rigorous theoretical framework of the generalized Kohn–Sham equation, our method is based on a range-split hybrid functional that uses exact long-range exchange. Its main novel feature is that the range-splitting parameter is not a universal constant but rather is determined from first principles, per system, based on satisfaction of the ionization potential theorem. For finite-sized objects, this DFT approach mimics successfully, to the best of our knowledge for the first time, the quasi-particle picture of many-body theory. Specifically, it allows for the extraction of both the fundamental and the optical gap from one underlying functional, based on the HOMO–LUMO gap of a ground-state DFT calculation and the lowest excitation energy of a linear-response time-dependent DFT calculation, respectively. In particular, it produces the correct optical gap for the difficult case of charge-transfer and charge-transfer-like scenarios, where conventional functionals are known to fail. In this perspective, we overview the formal and practical challenges associated with gap calculations, explain our new approach and how it overcomes previous difficulties, and survey its application to a variety of systems.

In conventional spectroscopy, transitions between electronic levels are governed by the electric dipole selection rule because electric quadrupole, magnetic dipole, and coupled electric dipole-magnetic dipole transitions are forbidden in a far field. We demonstrated that by using nanostructured electromagnetic fields, the selection rules of absorption spectroscopy could be fundamentally manipulated. We also show that forbidden transitions between discrete quantum levels in a semiconductor nanorod structure are allowed within the near-field of a noble metal nanoparticle. Atomistic simulations analyzed by an effective mass model reveal the breakdown of the dipolar selection rules where quadrupole and octupole transitions are allowed. Our demonstration could be generalized to the use of nanostructured near-fields for enhancing light-matter interactions that are typically weak or forbidden.

An ab initio variational grand-canonical electronic structure mean-field method, based on the Gibbs–Peierls–Bogoliubov minimum principle for the Gibbs free energy, is applied to the di-lithium (Li+Li) system at temperatures around T \approx 10,000 K and electronic chemical potential of μ \approx -0.1Eh. The method is an extension of the Hartree–Fock approach to finite temperatures. We first study the Li2 molecule at a frozen inter-nuclear distance of R = 3 \AA as a function of temperature. The mean-field electronic structure changes smoothly as temperature increases, up to 104 K, where a sharp spontaneous spin-polarization emerges as the variational mean-field solution. Further increase in the temperature extinguishes this polarization. We analyze the mean-field behavior using a correlated single-site Hubbard model and show it arises from an attempt of the mean-field to mimic the polarization of the spin–spin correlation function of the exact solution. Next, we keep constant the temperature at 104 K and examine the electronic structure as a function of inter-nuclear distance R. At R = 3.7 \AA, a crossing between two free energy states occurs: One state is “spin-unpolarized” (becomes lower in energy when R \ge 3.7 \AA), while the other is “spin polarized”. This crossing causes near-discontinuous jumps in calculated properties of the system and is associated with using the noninteracting electron character of our mean-field approach. Such problems will likely plague FT-DFT calculations as well. We use second-order perturbation theory (PT2) to study effects of electron correlation on the potential of mean force between the two colliding Li atoms. We find that PT2 correlation free energy at  104 K is larger than at 0 K and tends to restore the spin-polarized state as the lowest free energy solution.

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 single, 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.

In recent generalized Kohn-Sham (GKS) schemes for density functional theory (DFT) Hartree-Fock type exchange is important. In plane waves and grid approaches the high cost of exchange energy calculations makes these GKS considerably more expensive than Kohn-Sham DFT calculations. We develop a stochastic approach for speeding up the calculation of exchange for large systems. We show that stochastic error per particle does not grow and can even decrease with system size (at a given number of iterations). We discuss several alternative approaches and explain how these ideas can be included in the GKS framework.

A stochastic method is developed to calculate the multiexciton generation (MEG) rates in semiconductor nanocrystals (NCs). The numerical effort scales near-linearly with system size allowing the study of MEG rates up to diameters and exciton energies previously unattainable using atomistic calculations. Illustrations are given for CdSe NCs of sizes and energies relevant to current experimental setups, where direct methods require treatment of over 1011 states. The approach is not limited to the study of MEG and can be applied to calculate other correlated electronic processes.

Forster Resonance Energy Transfer (FRET) between fluorescent proteins (FPs) is widely used to construct fluorescent sensor proteins, to study intracellular protein-protein interactions and to monitor conformational changes in multidomain proteins. Although FRET depends strongly on the orientation of the transition dipole moments (TDMs) of the donor and acceptor fluorophores, this orientation dependence is currently not taken into account in FRET sensor design. Similarly, studies that use FRET to derive structural constrains typically assume a kappa(2) of 2/3 or use the TDM of green fluorescent protein, as this is the only FP for which the TDM has been determined experimentally. Here we used time-dependent density functional theory (TD-DFT) methods to calculate the TDM for a comprehensive list of commonly used fluorescent proteins. The method was validated against higher levels of calculation. Validation with model compounds and the experimentally determined TDM of GFP shows that the TDM is mostly determined by the structure of the pi-conjugated fluorophore and is insensitive to non-conjugated side chains or the protein surrounding. Our calculations not only provide TDM for most of the currently used FPs, but also suggest an empirical rule that can be used to obtain the TDMs for newly developed fluorescent proteins in the future.

The fundamental and optical gaps of relevant molecular systems are of primary importance for organic-based photovoltaics. Unfortunately, whereas optical gaps are accessible with time-dependent density functional theory (DFT), the highest-occupied - lowest-unoccupied eigenvalue gaps resulting from DFT calculations with semi-local or hybrid functionals routinely and severely underestimate the fundamental gaps of gas-phase organic molecules. Here, we show that a range-separated hybrid functional, optimally tuned so as to obey Koopmans' theorem, provides fundamental gaps that are very close to benchmark results obtained from many-body perturbation theory in the GW approximation. We then show that using this functional does not compromise the possibility of obtaining reliable optical gaps from time-dependent DFT. We therefore suggest optimally tuned range-separated hybrid functionals as a practical and accurate tool for DFT-based predictions of photovoltaically relevant and other molecular systems.

We address the conundrum posed by the well-known failure of time-dependent DFT (TDDFT) with conventional functionals for "charge-transfer-like" excitations in oligoacenes. We show that this failure is due to a small spatial overlap in orbitals obtained from the underlying single-electron orbitals by means of a unitary transformation. We further show that, as in true charge-transfer excitations, this necessarily results in failure of linear-response TDDFT with standard functionals. Range-separated hybrid functionals have been previously shown to mitigate such errors but at the cost of an empirically adjusted range-separation parameter. Here, we explain why this approach should succeed where conventional functionals fail. Furthermore, we show that optimal tuning of a range-separated hybrid functional, so as to enforce the DFT version of Koopmans' theorem, restores the predictive power of TDDFT even for such difficult cases, without any external reference data and without any adjustable parameters. We demonstrate the success of this approach on the oligoacene series and on related hydrocarbons. This resolves a long-standing question in TDDFT and extends the scope of molecules and systems to which TDDFT can be applied in a predictive manner.

A generalized Kohn-Sham (GKS) approach to density functional theory (DFT), based on the Baer-Neuhauser-Livshits range-separated hybrid, combined with ab initio motivated range-parameter tuning is used to study properties of water dimer and pentamer cations. The water dimer is first used as a benchmark system to check the approach. The present brand of DFT localizes the positive charge (hole), stabilizing the proton transferred geometry in agreement with recent coupled-cluster calculations. Relative energies of various conformers of the water dimer cation compare well with previously published coupled cluster results. The GKS orbital energies are good approximations to the experimental ionization potentials of the system. Low-lying excitation energies calculated from time-dependent DFT based on the present method compare well with recently published high-level "equation of motion-coupled-cluster" calculations. The harmonic frequencies of the water dimer cation are in good agreement with experimental and wave function calculations where available. The method is applied to study the water pentamer cation. Three conformers are identified: two are Eigen type and one is a Zundel type. The structure and harmonic vibrational structure are analyzed. The ionization dynamics of a pentamer water cluster at 0 K shows a fast <50 fs transient for transferring a proton from one of the water molecules, releasing a hydroxyl radical and creating a protonated tetramer carrying the excess hole.

Systematically varying the optical gap that is associated with charge-transfer excitations is an important step in the design of light-harvesting molecules. So far the guidance that time-dependent density functional theory could give in this process was limited by the traditional functionals' inability to describe charge-transfer excitations. We show that a nonempirical range-separated hybrid approach allows to reliably predict charge-transfer excitations for molecules of practically relevant complexity. Calculated absorption energies agree with measured ones. We predict from theory that by varying the number of thiophenes in donor-acceptor-donor molecules, the energy of the lowest optical absorption can be tuned to the lower end of the visible spectrum. Saturation sets in at about five thiophene rings. (C) 2011 American Institute of Physics. [doi:10.1063/1.3581788]

We present a broadly applicable, physically motivated, first-principles approach to determining the fundamental gap of finite systems from single-electron orbital energies. The approach is based on using a range-separated hybrid functional within the generalized Kohn-Sham approach to density functional theory. Its key element is the choice of a range-separation parameter such that Koopmans’ theorem for both neutral and anion is obeyed as closely as possible. We demonstrate the validity, accuracy, and advantages of this approach on first, second and third row atoms, the oligoacene family of molecules, and a set of hydrogen-passivated silicon nanocrystals. This extends the quantitative usage of density functional theory to an area long believed to be outside its reach.