Long‐range corrected functionals satisfy Koopmans' theorem: Calculation of correlation and relaxation energies

In this article, we show that the long‐range‐corrected (LC) density functionals LC‐BOP and LCgau‐BOP reproduce frontier orbital energies and highest‐occupied molecular orbital (HOMO)—lowest‐unoccupied molecular orbital (LUMO) gaps better than other density functionals. The negative of HOMO and LUMO energies are compared with the vertical ionization potentials (IPs) and electron affinities, respectively, using CCSD(T)/6‐311++G(3df,3pd) for 113 molecules, and we found LC functionals to satisfy Koopmans' theorem. We also report that the frontier orbital energies and the HOMO‐LUMO gaps of LC‐BOP and LCgau‐BOP are better than those of recently proposed ωM05‐D (Lin et al., J. Chem. Phys. 2012, 136 , 154109). We express the exact IP in terms of orbital relaxation, and correlation energies and hence calculate the relaxation and correlation energies for the same set of molecules. It is found that the LC functionals, in general, includes more relaxation effect than Hartree–Fock and more correlation effect than the other density functionals without LC scheme. Finally, we scan μ parameter in LC scheme from 0.1 to 0.6 bohr^?1 for the above test set molecules with LC‐BOP functional and found our parameter value, 0.47 bohr^?1, is usefully applicable to our tested systems. © 2013 Wiley Periodicals, Inc.     

Koopmans-like approximation in the Kohn-Sham method and the impact of the frozen core approximation on the computation of the reactivity parameters of the density functional theory

A Koopmans-like approximation is introduced in the spin-polarized version of the Kohn-Sham (KS) density functional theory to obtain a relation between KS orbital energies and vertical ionization potential and electron affinity. Expressions for reactivity indexes (like electronegativity, hardness, electrophilicity, and excitation energies) include KS frontier orbital energies and additional contributions associated with the self-interaction correction. Those reactivity parameters were computed with different exchange-correlation functionals to test the approach for a set of small molecules. The results show that the present approximation provides a better way to estimate hardness, electronegativity, and electrophilicity than just the use of frontier orbital energy values. However KS HOMO and LUMO energy gap gives a better agreement with excitation energies.     

Reaction energetics on long‐range corrected density functional theory: Diels–Alder reactions

The possibility of quantitative reaction analysis on the orbital energies of long‐range corrected density functional theory (LC‐DFT) is presented. First, we calculated the Diels–Alder reaction enthalpies that have been poorly given by conventional functionals including B3LYP functional. As a result, it is found that the long‐range correction drastically improves the reaction enthalpies. The barrier height energies were also computed for these reactions. Consequently, we found that dispersion correlation correction is also crucial to give accurate barrier height energies. It is, therefore, concluded that both long‐range exchange interactions and dispersion correlations are essentially required in conventional functionals to investigate Diels–Alder reactions quantitatively. After confirming that LC‐DFT accurately reproduces the orbital energies of the reactant and product molecules of the Diels–Alder reactions, the global hardness responses, the halves of highest occupied molecular orbital (HOMO)‐lowest unoccupied molecular orbital (LUMO) energy gaps, along the intrinsic reaction coordinates of two Diels–Alder reactions were computed. We noticed that LC‐DFT results satisfy the maximum hardness rule for overall reaction paths while conventional functionals violate this rule on the reaction pathways. Furthermore, our results also show that the HOMO‐LUMO gap variations are close to the reaction enthalpies for these Diels–Alder reactions. Based on these results, we foresee quantitative reaction analysis on the orbital energies. © 2012 Wiley Periodicals, Inc.     

About the compatibility between ansatzes and constraints for a local formulation of orbital‐free density functional theory

Functional properties that are exact for the Hohenberg–Kohn functional may turn into mutually exclusive constraints at a given level of ansatz. This is exemplarily shown for the local density approximation. Nevertheless, it is possible to reach exactly the Kohn–Sham data from an orbital‐free density functional framework based on simple one‐point functionals by starting from the Levy–Perdew–Sahni formulation. The energy value is obtained from the density‐potential pair, and therefore does not refer to the functional dependence of the potential expression. Consequently, the potential expression can be obtained from any suitable model and is not required to follow proper scaling behavior.     

Photo‐physical Properties of N‐methyl‐3,4‐fulleropyrrolidine and Its Derivatives: A DFT and TD‐DFT Investigation

A series of N‐methyl‐3,4‐fulleropyrrolidine (NMFP) derivatives were designed by selecting different π‐conjugated linkers and electron‐donating groups as D‐π‐A and D‐A systems. The optimised structures and photo‐physical properties of NMFP and its derivatives have been determined using density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) methods with the B3LYP functional and the 6‐31G basis set. According to the computation analysis, both the π‐conjugated linkers and the electron‐donating groups can influence the electronic and photo‐physical properties of the NMFP derivatives. Our calculated results demonstrated that the electron‐donating groups, with significant electron‐donating ability, had the tendency to increase the highest occupied molecular orbital (HOMO) energy. The π‐conjugated linkers with lower resonance energy decreased the lowest occupied molecular orbital (LUMO) energy and caused a significant decrease in the energy gap (E_g) between the E_HOMO and E_LUMO. A Natural Bond Orbital (NBO) analysis examines the effect of the electron‐donating group, π conjugated linker, and electron‐withdrawing group for these NMFP derivatives. For the NMFP derivatives, a projected density of state (PDOS) analysis demonstrated that the electron density of HOMO and LUMO are concentrated on the electron‐donating group and the π‐conjugated linker, respectively. A TD‐DFT/B3LYP calculation was performed to calculate the electronic absorption spectra of these NMFP derivatives. Both the electron‐donating group and the π‐conjugated linker contribute to the major absorption peaks, which are assigned as HOMO to LUMO transitions and are red‐shifted relative to those of non‐substituted NMFP.     

Determining the role of the underlying orbital‐dependence of PBE0‐DH and PBE‐QIDH double‐hybrid density functionals

We study the orbital‐dependence of three (parameter‐free) double‐hybrid density functionals, namely the PBE0‐DH, the PBE‐QIDH models, and the SOS1‐PBE‐QIDH spin‐opposite‐scaled variant of the latter. To do it, we feed all their energy terms with different sets of orbitals obtained previously from self‐consistent density functional theory calculations using several exchange‐correlation functionals (e.g., PBE, PBE0, PBEH&H), or directly with HF‐PBE orbitals, to see their effect on selected datasets for atomization and reaction energies, the latter proned to marked self‐interaction errors. We find that the PBE‐QIDH double‐hybrid model shows a great consistency, as the best results are always obtained for the set of orbitals corresponding to its hybrid scheme, which prompts us to recommend this model without any other fitting or reparameterization. © 2017 Wiley Periodicals, Inc.     

The exact Fermi potential yielding the Hartree–Fock electron density from orbital‐free density functional theory

The exact expression for the Fermi potential yielding the Hartree–Fock electron density within an orbital‐free density functional formalism is derived. The Fermi potential, which is defined as that part of the potential that depends on the particles’ nature, is in this context given as the sum of the Pauli potential and the exchange potential. The exact exchange potential for an orbital‐free density functional formalism is shown to be the Slater potential.     

Optimized effective potential from a correlated wave function: optimized effective potential-generalized valence bond (OEP-GVB)

The optimized effective potential (OEP) method allows orbital-dependent functionals to be used in density functional theory. Traditionally the orbital-dependent functional of interest has been the Hartree-Fock energy, leading to exact exchange density functional theory. Here we present results that use a generalized valence-bond (GVB) wave function, a multiconfigurational wave function that includes static correlation and dissociates to the proper limits. We demonstrate the effectiveness of the OEP-GVB method by showing the dissociation of H2 and the excitation spectrum of He.     

Electron smearing in DFT calculations: A case study of doxorubicin interaction with single‐walled carbon nanotubes

To address the choice of an appropriate value of electron smearing to facilitate self‐consistent field (SCF) convergence, we studied the interaction of doxorubicin with short armchair and zigzag single‐walled carbon nanotube models with closed caps, at the PWC/DNP level of density functional theory. By gradually reducing the electron smearing value from a large and most commonly used one of 0.005 Ha to zero (Fermi occupation), we monitored the changes in close contacts between the interacting species, total energy of the molecular system, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy and isosurfaces, HOMO‐LUMO gap energy, and plots of electrostatic potential. It became evident that the commonly used smearing values of ≥0.001 Ha can alter the results significantly (for example, by one order of magnitude for HOMO–LUMO gap energy). We suggest the setting of electron smearing value at 0.0001 Ha, which does not imply too high computation cost and can guarantee the results close to the ones obtained with Fermi occupation. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Numerically stable optimized effective potential method with balanced Gaussian basis sets

A solution to the long-standing problem of developing numerically stable optimized effective potential (OEP) methods based on Gaussian basis sets is presented by introducing an approach consisting of an exact exchange OEP method with an accompanying construction and balancing scheme for the involved auxiliary and orbital Gaussian basis sets that is numerically stable and that properly represents an exact exchange Kohn-Sham method. The method is a purely analytical method that does not require any numerical grid, scales like Hartree-Fock or B3LYP procedures, is straightforward to implement, and is easily generalized to take into account orbital-dependent density functionals other than the exact exchange considered in this work. Thus, the presented OEP approach opens the way to the development and application of novel orbital-dependent exchange-correlation functionals. It is shown that adequately taking into account the continuum part of the Kohn-Sham orbital spectrum is crucial for numerically stable Gaussian basis set OEP methods. Moreover, it is mandatory to employ orbital basis sets that are converged with respect to the used auxiliary basis representing the exchange potential. OEP calculations in the past often did not meet the latter requirement and therefore may have led to erroneously low total energies.     

Static and Frequency‐Dependent Dipole–Dipole Polarizabilities of All Closed‐Shell Atoms up to Radium: A Four‐Component Relativistic DFT Study

We test the performance of four‐component relativistic density functional theory by calculating the static and frequency‐dependent electric dipole–dipole polarizabilities of all (ground‐state) closed‐shell atoms up to Ra. We consider 12 nonrelativistic functionals, including three asymptotically shape‐corrected functionals, by using two smooth interpolation schemes introduced by the Baerends group: the gradient‐regulated asymptotic connection (GRAC) procedure and the statistical averaging of (model) orbital potentials (SAOP). Basis sets of doubly augmented triple‐zeta quality are used. The results are compared to experimental data or to accurate ab initio results. The reference static electric dipole polarizability of palladium has been obtained by finite‐field calculations using the coupled‐cluster singles, doubles, and perturbative triples method within this work. The best overall performance is obtained using hybrid functionals and their GRAC shape‐corrected versions. The performance of SAOP is among the best for nonhybrid functionals for Group 18 atoms but its precision degrades when considering the full set of atoms. In general, we find that conclusions based on results obtained for the rare‐gas atoms are not necessarily representative of the complete set of atoms. GRAC cannot be used with effective core potentials since the asymptotic correction is switched on in the core region.     

A Simple, Exact Density-Functional-Theory Embedding Scheme

Density functional theory (DFT) provides a formally exact framework for quantum embedding. The appearance of nonadditive kinetic energy contributions in this context poses significant challenges, but using optimized effective potential (OEP) methods, various groups have devised DFT-in-DFT methods that are equivalent to Kohn-Sham (KS) theory on the whole system. This being the case, we note that a very considerable simplification arises from doing KS theory instead. We then describe embedding schemes that enforce Pauli exclusion via a projection technique, completely avoiding numerically demanding OEP calculations. Illustrative applications are presented using DFT-in-DFT, wave-function-in-DFT, and wave-function-in-Hartree-Fock embedding, and using an embedded many-body expansion.     

Ab initio investigation of 2,2′‐bis(4‐trifluoromethylphenyl)‐5,5′‐bithiazole for the design of efficient organic field‐effect transistors

The initial molecular structure of 2,2′‐bis(4‐trifluoromethylphenyl)‐ 5,5′‐bithiazole has been optimized in the ground state using density functional theory (DFT). The distribution patterns of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) have also been evaluated. To shed light on the charge transfer properties, we have calculated the reorganization energy of electron λ_e, the reorganization energy of hole λ_h, adiabatic electron affinity (EA_a), vertical electron affinity (EA_v), adiabatic ionization potential (IP_a), and vertical ionization potential (IP_v) using DFT. Based on the evaluation of hole reorganization energy, λ_h, and electron reorganization energy, λ_e, it has been predicted that 2,2′‐bis(4‐trifluoromethylphenyl)‐5,5′‐bithiazole would be a better electron transport material. Finally, the effect of electric field on the HOMO, LUMO, and HOMO–LUMO gap were observed to check its suitability for the use as a conducting channel in organic field‐effect transistors. © 2015 Wiley Periodicals, Inc.     

Exact electronic properties in the classically forbidden region of a metal surface

We derive exact properties of the inhomogeneous electron gas in the asymptotic classically forbidden region at a metal–vacuum interface within the framework of local effective potential energy theory. We derive a new expression for the asymptotic structure of the Kohn–Sham density functional theory (KS‐DFT) exchange‐correlation potential energy v_xc(r) in terms of the irreducible electron self‐energy. We also derive the exact asymptotic structure of the orbitals, density, the Dirac density matrix, the kinetic energy density, and KS exchange energy density. We further obtain the exact expression for the Fermi hole and demonstrate its structure in this asymptotic limit. The exchange‐correlation potential energy is derived to be v_xc(z → ∞) = ?α_KS,xc/z, and its exchange and correlation components to be v_x(z → ∞) = ?α_KS,x/z and v_c(z → ∞) = ?α_KS,c/z, respectively. The analytical expressions for the coefficients α_KS,xc and α_KS,x show them to be dependent on the bulk‐metal Wigner–Seitz radius and the barrier height at the surface. The coefficient α_KS,c = 1/4 is determined in the plasmon‐pole approximation and is independent of these metal parameters. Thus, the asymptotic structure of v_xc(z) in the vacuum region is image‐potential‐like but not the commonly accepted one of ?1/4z. Furthermore, this structure depends on the properties of the metal. Additionally, an analysis of these results via quantal density functional theory (Q‐DFT) shows that both the Pauli W_x(z → ∞) and lowest‐order correlation‐kinetic W(z → ∞) components of the exchange potential energy v_x(z → ∞), and the Coulomb W_c(z → ∞) and higher‐order correlation‐kinetic components of the correlation potential energy v_c(z → ∞), all contribute terms of O(1/z) to the structure. Hence correlations attributable to the Pauli exclusion principle, Coulomb repulsion, and correlation‐kinetic effects all contribute to the asymptotic structure of the effective potential energy at a metal surface. The relevance of the results derived to the theory of image states and to KS‐DFT is also discussed. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Coupled‐cluster reaction barriers of : An application of the coupled‐cluster//Kohn–Sham density functional theory model chemistry

In this work, we report a theoretical investigation concerning the use of the popular coupled‐cluster//Kohn‐Sham density functional theory (CC//KS‐DFT) model chemistry, here applied to study the entrance channel of the reaction, namely by comparing CC//KS‐DFT calculations with KS‐DFT, MRPT2//CASSCF, and CC//CASSCF results from our previous investigations. This was done by performing single point energy calculations employing several coupled cluster methods and using KS‐DFT geometries optimized with six different functionals, while conducting a detailed analysis of the barrier heights and topological features of the curves and surfaces here obtained. The quality of this model chemistry is critically discussed in the context of the title reaction and also in a wider context. © 2013 Wiley Periodicals, Inc.     

Analytic derivatives for the XYG3 type of doubly hybrid density functionals: Theory,implementation, and assessment

We present a theoretical development of the equations required to perform an analytic geometry optimization of a molecular system using the XYG3 type of doubly hybrid (xDH) functionals. In contrast to the well‐established B2PLYP type of DH functionals, the energy expressions in the xDH functionals are constructed by using density and orbital information from another standard Kohn–Sham (KS) functional (e.g., B3LYP) for doing the self‐consistent field calculations. Thus, the xDH functionals are nonvariational in both the hybrid density functional part and the second‐order perturbation part, each of which requires formally to solve a coupled‐perturbed KS equation. An implementation is reported here which combines the two parts by defining a total Lagrangian such that only a single set of the Z‐vector equations need to be solved. The computational cost with our implementation is of the same order as those for the conventional Møller–Plesset theory to the second order (MP2) and B2PLYP. Systematic test calculations are provided for covalently bonded molecules as well as compounds involving the intramolecular nonbonded interactions for the main group elements. Satisfactory performance of the xDH functionals demonstrates that the extra computer time on top of the conventional KS procedure is well‐invested, in particular, when the standard KS functionals and MP2 as well, are problematic. © 2013 Wiley Periodicals, Inc.     

Exchange and correlation energy in density functional theory

Several different versions of density functional theory (DFT) that satisfy Hohenberg–Kohn theorems are characterized by different definitions of a reference or model state determined by an N‐electron ground state. A common formalism is developed in which exact Kohn–Sham equations are derived for standard Kohn–Sham theory, for reference‐state density functional theory, and for unrestricted Hartree–Fock (UHF) theory considered as an exactly soluble model Hohenberg–Kohn theory. A natural definition of exchange and correlation energy functionals is shown to be valid for all such theories. An easily computed necessary condition for the locality of exchange and correlation potentials is derived. While it is shown that in the UHF model of DFT the optimized effective potential (OEP) exchange satisfies this condition by construction, the derivation shows that this condition is not, in general, sufficient to define an exact local exchange potential. It serves as a test to eliminate proposed local potentials that are not exact for ground states. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 521–525, 2000     

Comparing ab initio density-functional and wave function theories: the impact of correlation on the electronic density and the role of the correlation potential

The framework of ab initio density-functional theory (DFT) has been introduced as a way to provide a seamless connection between the Kohn-Sham (KS) formulation of DFT and wave-function based ab initio approaches [R. J. Bartlett, I. Grabowski, S. Hirata, and S. Ivanov, J. Chem. Phys. 122, 034104 (2005)]. Recently, an analysis of the impact of dynamical correlation effects on the density of the neon atom was presented [K. Jankowski, K. Nowakowski, I. Grabowski, and J. Wasilewski, J. Chem. Phys. 130, 164102 (2009)], contrasting the behaviour for a variety of standard density functionals with that of ab initio approaches based on second-order M?ller-Plesset (MP2) and coupled cluster theories at the singles-doubles (CCSD) and singles-doubles perturbative triples [CCSD(T)] levels. In the present work, we consider ab initio density functionals based on second-order many-body perturbation theory and coupled cluster perturbation theory in a similar manner, for a range of small atomic and molecular systems. For comparison, we also consider results obtained from MP2, CCSD, and CCSD(T) calculations. In addition to this density based analysis, we determine the KS correlation potentials corresponding to these densities and compare them with those obtained for a range of ab initio density functionals via the optimized effective potential method. The correlation energies, densities, and potentials calculated using ab initio DFT display a similar systematic behaviour to those derived from electronic densities calculated using ab initio wave function theories. In contrast, typical explicit density functionals for the correlation energy, such as VWN5 and LYP, do not show behaviour consistent with this picture of dynamical correlation, although they may provide some degree of correction for already erroneous explicitly density-dependent exchange-only functionals. The results presented here using orbital dependent ab initio density functionals show that they provide a treatment of exchange and correlation contributions within the KS framework that is more consistent with traditional ab initio wave function based methods.     

Accelerating the convergence of the total energy evaluation in density functional theory calculations

A special feature of the Strutinsky shell correction method (SCM) [D. Ullmo et al., Phys. Rev. B 63, 125339 (2001)] and the recently proposed orbital-corrected orbital-free density functional theory (OO-DFT) [B. Zhou and Y. A. Wang, J. Chem. Phys. 124, 081107 (2006)] is that the second-order corrections are incorporated in the total energy evaluation. In the SCM, the series expansion of the total electronic energy is essentially the Harris functional with its second-order correction. Unfortunately, a serious technical problem for the SCM is the lack of the exact Kohn-Sham (KS) density rho KS(r) required for the evaluation of the second-order correction. To overcome this obstacle, we design a scheme that utilizes the optimal density from a high-quality density mixing scheme to approximate rho KS(r). Recently, we proposed two total energy density functionals, i.e., the Zhou-Wang-lambda (ZW lambda) and the Wang-Zhou-alpha (WZ alpha) functionals, for use in the OO-DFT method. If the two interpolation parameters, lambda and alpha, are chosen to allow the second-order errors of the ZW lambda and the WZ alpha functionals to vanish, these two functionals reduce to the Hohenberg-Kohn-Sham functional with its second-order correction. Again, the optimal density from a high-quality density mixing scheme is used to approximate rho KS(r) in the evaluation of lambda and alpha. This approach is tested in iterative KS-DFT calculations on systems with different chemical environments and can also be generalized for use in other iterative first-principles quantum chemistry methods.     

Molecular design of a π‐conjugated single‐chain electronically conductive polymer

This study demonstrates that single‐chain π‐conjugated systems can be made electrically conductive by modifying the molecular structures of both ends of the oligomers making up a polymer. That is, the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gaps of a fairly long polyyne‐type oligomer with appropriately modified molecular structures at both ends are found to be on the order of thermal energy by calculations using density functional theory (DFT) with B3LYP functionals. This result applies to molecular structures with characteristic bond alternations. The peculiar bond alternations are caused by competition between two effects of the bond alternations of the two mutually perpendicular π‐conjugated systems, which partially cancel each other out. It is probable that we can design one‐dimensional polymers with HOMO–LUMO gaps small enough to be conductive by combining the above‐mentioned oligomers with each other as monomer units in the polymer. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006