# John P. Perdew's research while affiliated with Temple University and other places

## Publications (460)

Preprint
Full-text available
The SCAN (strongly constrained and appropriately normed) meta-generalized gradient approximation (meta-GGA), which satisfies all 17 exact constraints that a meta-GGA can satisfy, accurately describes equilibrium bonds that are normally correlated. With symmetry breaking, it also accurately describes some sd equilibrium bonds that are strongly corre...
Article
Full-text available
In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchan...
Article
We derive and motivate a Laplacian-level, orbital-free meta-generalized-gradient approximation (LL-MGGA) for the exchange-correlation energy, targeting accurate ground-state properties of sp and sd metallic condensed matter, in which the density functional for the exchange-correlation energy is only weakly nonlocal due to perfect long-range screeni...
Article
SCAN+rVV10 has been demonstrated to be a versatile van der Waals (vdW) density functional that delivers good predictions of both energetic and structural properties for many types of bonding. Recently, the r2SCAN functional was devised as a revised form of SCAN with improved numerical stability. In this work, we refit the rVV10 functional to optimi...
Preprint
Full-text available
In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchan...
Preprint
A central aim of materials discovery is an accurate and numerically reliable description of thermodynamic properties, such as the enthalpies of formation and decomposition. The r$^2$SCAN revision of the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation (meta-GGA) balances numerical stability with high gene...
Preprint
Delocalization errors, such as charge-transfer and self-interaction errors, plague computationally-efficient and otherwise-accurate density functional approximations (DFAs). Evaluating a semi-local DFA non-self-consistently on the Hartree-Fock (HF) density is often recommended as a computationally inexpensive remedy for delocalization errors. This...
Preprint
Ground-state Kohn-Sham density functional theory provides, in principle, the exact ground-state energy and electronic spin-densities of real interacting electrons in a static external potential. In practice, the exact density functional for the exchange-correlation (xc) energy must be approximated in a computationally efficient way. About twenty ma...
Article
Density functional theory (DFT) is the most widely used electronic structure method, due to its simplicity and cost effectiveness. The accuracy of a DFT calculation depends not only on the choice of the density functional approximation (DFA) adopted but also on the electron density produced by the DFA. SCAN is a modern functional that satisfies all...
Preprint
Lieb and Oxford (1981) derived rigorous lower bounds, in the form of local functionals of the electron density, on the indirect part of the Coulomb repulsion energy. The greatest lower bound for a given electron number N depends monotonically upon N, and the N-> infinity limit is a bound for all N. These bounds have been shown to apply to the exact...
Preprint
Full-text available
In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchan...
Preprint
Full-text available
In a data-driven paradigm, machine learning (ML) is the central component for developing accurate and universal exchange-correlation (XC) functionals in density functional theory (DFT). It is well known that XC functionals must satisfy several exact conditions and physical constraints, such as density scaling, spin scaling, and derivative discontin...
Preprint
Full-text available
SCAN+rVV10 has been demonstrated to be a versatile van der Waals (vdW) density functional that delivers good predictions of both energetic and structural properties for many types of bonding. Recently, the r²SCAN functional has been devised as a revised form of SCAN with improved numerical stability. In this work, we refit the rVV10 functional to o...
Article
Density functional theory (DFT)-based descriptions of the adsorption of small molecules on transition metal ions are prone to self-interaction errors. Here, we show that such errors lead to a large over-estimation of adsorption energies of small molecules on Cu ⁺ , Zn ⁺ , Zn ²⁺ , and Mn ⁺ in local spin density approximation (LSDA) and Perdew, Burke...
Preprint
Full-text available
Density functional theory (DFT) is the most widely used electronic structure method, due to its simplicity and cost effectiveness. The accuracy of a DFT calculation de- pends not only on the choice of the density functional approximation (DFA) adopted but also on the electron density produced by the DFA. SCAN is a modern functional that satisfies a...
Preprint
We derive and motivate a Laplacian-level meta-GGA (LL-MGGA) targeting accurate ground-state properties of metallic solids. Our model for the orbital-free kinetic energy density restores the fourth-order gradient expansion for exchange to the r2SCAN meta-GGA [Furness et al, J. Phys. Chem. Lett. 11, 8208 (2020)], yielding a LL-MGGA we call OFR2. OFR2...
Article
We propose a spatially and temporally nonlocal exchange correlation (XC) kernel for the spin-unpolarized fluid phase of ground-state jellium for use in time-dependent density functional and linear response calculations. The kernel is constructed to satisfy known properties of the exact XC kernel to accurately describe the correlation energies of bu...
Article
The SCAN meta-GGA exchange-correlation functional [Phys. Rev. Lett. 115, 036402 (2015)] is constructed as a chemical environment-determined interpolation between two separate energy densities: one describes single orbital electron densities accurately, and another describes slowly-varying densities accurately. To conserve constraints known for the...
Article
Machine-learning creates a density functional that accounts for fractional charge and spin
Article
The atomization energies of molecules from first-principles density functional approximations improve from the local spin-density approximation (LSDA) to the Perdew-Burke-Ernzerhof (PBE)) generalized gradient approximation (GGA) to the strongly constrained and appropriately normed (SCAN) meta-GGA, and their sensitivities to non-spherical components...
Article
Full-text available
Density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. Here, we present density-corrected SCA...
Preprint
Density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. Here, we present density-corrected SCA...
Preprint
Full-text available
Density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. Here, we present density-corrected SCA...
Article
Full-text available
The discovery of solid-phase, inexpensive transition-metal-based water oxidation catalysts is a central goal for renewable energy, and has led to a general consensus that a partially populated metal eg d-electronic state is desirable, leading to favorable catalysis for certain elements in specific oxidation states. In manganese systems, the key spe...
Preprint
Full-text available
The SCAN meta-GGA exchange-correlation functional [Phys. Rev. Lett. 115, 036402 (2015)] is constructed as a chemical environment-determined interpolation between two separate energy densities: one describes single orbital electron densities accurately, and another describes slowly-varying densities accurately. To conserve constraints known for the...
Preprint
Full-text available
The atomization energies of molecules from first-principles density functional approximations improve from the local spin-density approximation (LSDA) to the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) to the strongly constrained and appropriately normed (SCAN) meta-GGA, and their sensitivities to non-spherical components...
Article
Full-text available
Within the framework of Kohn–Sham density functional theory (DFT), the ability to provide good predictions of water properties by employing a strongly constrained and appropriately normed (SCAN) functional has been extensively demonstrated in recent years. Here, we further advance the modeling of water by building a more accurate model on the fourt...
Article
Fermi orbital descriptors (FODs) play a key role in Fermi-Löwdin orbital self-interaction correction (FLOSIC) calculations used to remove self-interaction from approximate density functionals. Optimal FODs are obtained by minimizing the self-interaction-corrected total energy, and, in this process, identifying initial sets of FODs becomes crucial....
Preprint
Kohn-Sham density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. The recent development of th...
Preprint
Full-text available
Kohn-Sham density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. The recent development of th...
Preprint
Full-text available
Kohn-Sham density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. The recent development of th...
Preprint
Kohn-Sham density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. The recent development of th...
Preprint
We propose a spatially and temporally nonlocal exchange-correlation (xc) kernel for the spin-unpolarized fluid phase of ground-state jellium, for use in time-dependent density functional and linear response calculations. The kernel is constructed to satisfy known properties of the exact xc kernel, to accurately describe the correlation energies of...
Article
We extend the damped Zaremba-Kohn model (dZK) for long-range dispersion interaction between a molecule and a planar surface [J. Tao, H. Tang, A. Patra, P. Bhattarai, and J. P. Perdew, Phys. Rev. B 97, 165403 (2018)] to molecules adsorbed on a curved cylindrical surface, and employ this extended model as an additive correction to the semilocal densi...
Preprint
Full-text available
Within the framework of Kohn-Sham density functional theory (DFT), the ability to provide good predictions of water properties by employing a strongly constrained and appropriately normed (SCAN) functional has been extensively demonstrated in recent years. Here, we further advance the modeling of water by building a more accurate model on the fourt...
Article
Full-text available
We study the importance of self-interaction errors in density functional approximations for various water–ion clusters. We have employed the Fermi–Löwdin orbital self-interaction correction (FLOSIC) method in conjunction with the local spin-density approximation, Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation (GGA), and strongly co...
Article
The Perdew-Zunger self-interaction correction (PZ-SIC) improves the performance of density functional approximations for the properties that involve significant self-interaction error (SIE), as in stretched bond situations, but overcorrects for equilibrium properties where SIE is insignificant. This overcorrection is often reduced by local scaling...
Article
We combine a regularized variant of the strongly constrained and appropriately normed semilocal density functional [J. Sun, A. Ruzsinszky, and J. P. Perdew, Phys. Rev. Lett. 115, 036402 (2015)] with the latest generation semi-classical London dispersion correction. The resulting density functional approximation r²SCAN-D4 has the speed of generalize...
Article
Full-text available
Classical turning surfaces of Kohn–Sham potentials separate classically allowed regions (CARs) from classically forbidden regions (CFRs). They are useful for understanding many chemical properties of molecules but need not exist in solids, where the density never decays to zero. At equilibrium geometries, we find that CFRs are absent in perfect met...
Article
Significance The ground state of a quantum mechanical system is the lowest-energy eigenstate of the Hamiltonian. In isolation, it persists unchanged forever, with symmetries dictated by those of the Hamiltonian. But near-eigenstates of broken symmetry can persist for long times, even on the scale of human measurement. The appearance of broken symme...
Article
The Perdew–Zunger self-interaction correction (PZ-SIC) removes unphysical electron self-interaction from calculations employing standard density functional approximations. Doing so improves many computed properties, bringing them into better agreement with experimental observations or with results from high-level quantum chemistry calculations. How...
Preprint
Full-text available
The Perdew-Zunger self-interaction correction(PZ-SIC) improves the performance of density functional approximations(DFAs) for the properties that involve significant self-interaction error(SIE), as in stretched bond situations, but overcorrects for equilibrium properties where SIE is insignificant. This overcorrection is often reduced by LSIC, loca...
Preprint
Full-text available
We study the importance of self-interaction errors in density functional approximations for various water-ion clusters. We have employed the Fermi-L\"owdin orbital self-interaction correction (FLOSIC) method in conjunction with LSDA, PBE, and SCAN to describe binding energies of hydrogen-bonded water-ion clusters, \textit{i.e.}, water-hydronium, wa...
Preprint
Full-text available
We combine a regularized variant of the strongly constrained and appropriately normed semilocal density functional [J. Sun, A. Ruzsinszky, and J. P. Perdew, Phys. Rev. Lett. 115, 036402 (2015)] with the latest generation semi-classical London dispersion correction. The resulting density functional approximation r2SCAN-D4 has the speed of generalize...
Article
The recently proposed rSCAN functional [J. Chem. Phys. 150, 161101 (2019)] is a regularized form of the SCAN functional [Phys. Rev. Lett. 115, 036402 (2015)] that improves SCAN's numerical performance at the expense of breaking constraints known from the exact exchange-correlation functional. We construct a new meta-generalized gradient approximati...
Article
Exact density functionals for the exchange and correlation energies are approximated in practical calculations for the ground-state electronic structure of a many-electron system. An important exact constraint for the construction of approximations is to recover the correct non-relativistic large-Z expansions for the corresponding energies of neutr...
Preprint
Full-text available
The recently proposed rSCAN functional [J. Chem. Phys. 150, 161101 (2019)] is a regularized form of the SCAN functional [Phys. Rev. Lett. 115, 036402 (2015)] that improves SCAN's numerical performance at the expense of breaking constraints known from the exact exchange-correlation functional. We construct a new meta-generalized gradient approximati...
Preprint
Full-text available
Strong correlations within a symmetry-unbroken ground-state wavefunction can show up in approximate density functional theory as symmetry-broken spin-densities or total densities, which are sometimes observable. They can arise from soft modes of fluctuations (sometimes collective excitations) such as spin-density or charge-density waves at non-zero...
Preprint
Full-text available
Exact density functionals for the exchange and correlation energies are approximated in practical calculations for the ground-state electronic structure of a many-electron system. An important exact constraint for the construction of approximations is to recover the correct non-relativistic large-$Z$ expansions for the corresponding energies of neu...
Preprint
Classical turning surfaces of Kohn-Sham potentials, separating classically-allowed regions (CARs) from classically-forbidden regions (CFRs), provide a useful and rigorous approach to understanding many chemical properties of molecules. Here we calculate such surfaces for several paradigmatic solids. Our study of perfect crystals at equilibrium geom...
Article
According to time-dependent density functional theory, the exact exchange-correlation kernel fxc(n,q,ω) for wave vector q and frequency ω determines not only the ground-state energy but also the excited-state energies/lifetimes and time-dependent linear density response of an electron gas of uniform density n=3/(4πrs3). Here we propose a parametriz...
Article
Full-text available
The Perdew–Zunger (PZ) self-interaction correction (SIC) was designed to correct the one-electron limit of any approximate density functional for the exchange–correlation (xc) energy, while yielding no correction to the exact functional. Unfortunately, it spoils the slowly varying (in space) limits of the uncorrected approximate functionals, where...
Article
Standard density functionals like Perdew-Burke-Ernzerhof (PBE) or Strongly Constrained and Appropriately Normed (SCAN) need a correction to account for long-range van der Waals (vdW) interaction. The damped Zaremba-Kohn model (dZK) [J. Tao, H. Tang, A. Patra, P. Bhattarai, and J. P. Perdew, Phys. Rev. B 97, 165403 (2018)] starts from a formula for...
Article
Significance Self-interaction error has long been identified as one of the limitations of practical density functional approximations. This error originates in the inability of approximate density functionals to exactly cancel self-Coulomb and self-exchange–correlation for all one-electron densities. Self-interaction error can be subtracted from an...
Article
Poly(p-phenylene terephthalamide) (PPTA) exhibits van der Waals (vdW) bonding along its a axis, hydrogen bonding along its b axis, and covalent bonding along its c axis. We explore the structural and mechanical properties of PPTA using density functional theory with various functionals including LDA, PBE, PBE+rVV10L, SCAN, and SCAN+rVV10, compared...
Preprint
Full-text available
The Perdew-Zunger(PZ) self-interaction correction (SIC) was designed to correct the one-electron limit of any approximate density functional for the exchange-correlation (xc) energy, while yielding no correction to the exact functional. Unfortunately, it spoils the slowly-varying-in-space limits of the uncorrected approximate functionals, where tho...
Preprint
Full-text available
According to time-dependent density functional theory, the exact exchange-correlation kernel f$_{xc}$(n, q, $\omega$) determines not only the ground-state energy but also the excited-state energies/lifetimes and time-dependent linear density response of an electron gas of uniform density n $=$ 3/(4$\pi$r$^3_s$). Here we propose a parametrization of...
Article
Silver nanostructures with hierarchical porosities of multiple length scales have been synthesized through electrochemical reduction of silver benzenethiolate nanoboxes. The porous Ag nanostructures exhibit superior catalytic performance towards electrochemical reduction of CO2. The Faradaic efficiency of reducing CO2 to CO can be close to 100% at...
Article
The classical Kohn–Sham turning radius Rt of an atom can be defined as the radius where the Kohn–Sham potential is equal to the negative ionization potential of the atom, i.e., where vs(Rt) = ϵh. It was recently shown [E. Ospadov et al., Proc. Natl. Acad. Sci. U. S. A. 115, E11578–E11585 (2018)] to yield chemically relevant bonding distances, in li...
Article
Significance High-temperature superconductivity, first discovered in materials with copper-oxide planes, is still not well understood. Cuprates exhibit complex phase diagrams under temperature and doping and have not been amenable to first-principles description using previous density functionals, but the recent SCAN functional correctly predicts m...
Article
Full-text available
Self-interaction (SI) error, which results when exchange-correlation contributions to the total energy are approximated, limits the reliability of many density functional approximations. The Perdew-Zunger SI correction (PZSIC), when applied in conjunction with the local spin density approximation (LSDA), improves the description of many properties,...
Preprint
Full-text available
Self-interaction (SI) error, which results when exchange-correlation contributions to the total energy are approximated, limits the reliability of many density functional approximations. The Perdew-Zunger SI correction (PZSIC), when applied in conjunction with the local spin density approximation (LSDA), improves the description of many properties,...
Article
Realization of half-metallicity with a sizable minority-spin gap and ferromagnetic ordering has been a central research emphasis in the development of next-generation spintronic devices. To date, only three-dimensional half-metals have been achieved experimentally, while their counterparts based on two-dimensional (2D) materials remain to be materi...
Preprint
The classical turning radius Rt of an atom can be defined as the radius where the KS potential is equal to the negative ionisation potential of the atom, i.e. where v_s(R_t)=\epsilon_h. It was recently shown [P.N.A.S. 115, E11578 (2018)] to yield chemically relevant bonding distances, in line with known empirical values. In this work we show that e...
Article
The random-phase approximation (RPA) is exact for the exchange energy of a many-electron ground state, but RPA makes the correlation energy too negative by about 0.5 eV/electron. That large short-range error, which tends to cancel out of isoelectronic energy differences, is largely corrected by an exchange-correlation kernel, or (as in RPA+) by an...
Article
A nanoscale junction that allows the measurement of the conductivity of a single molecule along different directions was devised as described by E. Borguet and co‐workers in their Research Article (DOI: 10.1002/anie.201903898). The conductance of the planar molecule trimesic acid is about 400 times higher when the molecule lies flat on the surface...
Article
Nanoskalige Kontakte, mit denen die Leitfähigkeit eines einzelnen Moleküls in verschiedene Richtungen gemessen werden kann, werden von E. Borguet et al. in ihrem Forschungsartikel (DOI: 10.1002/ange.201903898) beschrieben. Wenn das planare Molekül Trimesinsäure flach auf dem Substrat aufliegt, ist die Leitfähigkeit etwa 400‐mal höher als bei einer...