Excited-state Density Functional Theory Research Articles

Using ground state and excited state density functional theory to decipher 3d dopant defects in GaN

Using ground state density functional theory (DFT) and implementing an occupation-constrained DFT (occ-DFT) for self-consistent excited state calculations, we decipher the electronic structure of the Mn dopant and other 3ddefects in GaN across the band gap. Our analysis, validated with broad agreement with defect levels (ground-state calculations) and photoluminescence data (excited-state calculations), mandates reinterpretation and reassignment of 3ddefect data in GaN. The MnGadefect is determined to span stable charge states from (1-) inn-type GaN through (2+) inp-type GaN. The Mn(2+) is predicted to be ad2ground state spin triplet defect with a singlet excited state, isoelectronic with the defect associated with the 1.19 eV photoluminescence inn-type GaN. The combined analysis of defect levels and excited states invites reassessment of alld2-capable dopants in GaN. We demonstrate that the 1.19 eV defect, a candidate defect for optically controlled quantum applications, cannot be the Cr(1+) assumed in literature and instead must be the V(0). The combined ground-state/excited-state DFT analysis is shown to be able to chemically fingerprint defects.

Azaindolizine proton cranes attached to 7-hydroxyquinoline and 3-hydroxypyridine: a comparative theoretical study.

Theoretical design of several proton cranes, based on 7-hydroxyquinoline and 3-hydroxypyridine as proton-transfer frames, has been attempted using ground and excited-state density functional theory (DFT) calculations in various environments. Imidazo[1,2-a]pyridine, pyrazolo[1,5-a]pyridine and benzimidazole were considered as proton crane units. The proton crane action requires the existence of a single enol-like form in the ground state, which under excitation goes to the end keto-like one through a series of consecutive excited-state intramolecular proton transfers (ESIPT) and twisting steps with the participation of a crane unit, resulting in a long-range intramolecular proton transfer. The results suggest that 3-hydroxypyridine is not suitable for a proton-transfer frame and 8-(imidazo[1,2-a]pyridin-2-yl)quinolin-7-ol and 8-(pyrazolo[1,5-a]pyridin-2-yl)quinolin-7-ol behave as non-conjugated proton cranes, instead of tautomeric re-arrangement in the latter, which was thought to be possible.

Molecule Dipole and Steric Hindrance Engineering to Modulate Electronic Structure of PTCDA/PTA for Highly Efficient Photocatalytic Hydrogen Evolution and Antibiotics Degradation

AbstractInsufficient charge separation and slow exciton transport severely limit the utilization of perylene‐plane‐based organic photocatalysts. Herein, a novel PTCDA/PTA (perylene‐3,4,9,10‐tetracarboxylic dianhydride/perylenetetracarboxylic acid) is successfully prepared for the first time by the in situ crystallization of PTA on the surface of PTCDA through π–π interaction. The PTCDA/PTA loading with 8%PTCDA showed the optimum photocatalytic performance. The photocatalytic H2 evolution rate reached 45.06 mmol g−1 h−1, which is 1.93‐fold and 4506.00‐fold higher than that of pure PTA and PTCDA. Meanwhile, it also exhibited excellent antibiotics photodegradation activities, in which both the removal efficiency of tetracycline hydrochloride (TC‐HCl) and ofloxacin (OFL) are more over 90% within 30 min. By modulating the structures of perylene plane, the steric hindrance and internal dipole moments can be precisely tuned. These lead to the change of stacking mode, promoting the degree of π–π stacking and formation of strong internal electric field, while improved the photocatalytic activity. Excited state density functional theory (DFT) calculations unveil the redistribution of electron‐hole pairs, which obeys a type II mechanism. The proposed photocatalytic mechanism is determined by liquid chromatography‐mass spectrometry (LC‐MS). Besides, the toxicities of the degradation products are also evaluated. The work provides useful strategy for the design of high‐performance and multifunctional photocatalysts toward water remediation and energy production.

Electron donor–acceptor type delayed fluorescence emitters with inverted singlet and triplet excited states

Emitters having a negative energy difference between their lowest singlet and triplet excited states are promising candidates for developing next-generation organic light-emitting diodes (OLEDs) because their inverted singlet and triplet (IST) excited states enable exothermic reverse intersystem crossing, which results in a fast rate constant for reverse intersystem crossing and facilitates the efficient harvesting of triplet excitons. This study reports the development of organic emitters comprising 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene as an electron acceptor and 10H-spiro[acridine-9,9′-fluorene] as an electron donor that exhibit IST-excited states. We confirmed the presence of IST excited states in our emitters using photoluminescence spectroscopy, time-correlated single-photon counting, and excited-state density functional theory calculations. In addition, by varying the number of electron donors and the dihedral angles between the electron donor and acceptor, we identified the underlying reasons for the inversion of the singlet and triplet states. Furthermore, we achieved high external quantum efficiencies of up to 30 % by utilizing the IST emitters as emitting layers in OLEDs.

Enhancement of intrinsic optical transitions in silicon nanocrystals by state localization

Silicon photoluminescence and lasing have been critical issues to breakthrough bottlenecks in the understanding of luminescence mechanisms. Unfortunately, long-standing disputes about the exciton recombination mechanism and fluorescence lifetime remain unresolved, especially about whether silicon nanocrystals (Si NCs) can realize fast direct-bandgap-like optical transitions. Here, using ground-state and excited-state density functional theory (DFT), we obtained intrinsic phonon-free optical transitions at sizes from Si22 to Si705, showing that very small Si NCs can realize a strong direct optical transition. Orbital labeling results show that this rapid transition does not come from the {\Gamma}-{\Gamma} -like transition, contrary to the conclusions from the effective mass approximation (EMA) and that {\Gamma}-X mixing leads to a quasi-direct bandgap. This anomalous transition is particularly intense with decreasing size (or enhancement of quantum confinement). By investigating electron and hole distributions generated in the optical transition, localized state-induced enhanced emission (LIEE) in Si NCs was proposed. Quantum confinement (QC) distorts the excited-state electron spatial distribution by localizing Bloch waves into the NC core, resulting in increased hole and electron overlap, thus inducing a fast optical process. This work resolves important debates and proposes LIEE to explain the anomalous luminescence--a phase transition from weak (or none) luminescent state to strong optical transition, which will aid attempts at realizing high-radiative-rate NCs materials and application-level Si lasers.

Absorption and Photoluminescence of Silicon Nanocrystals Investigated by Excited State DFT: Role of Embedding Dielectric and Defects

Absorption and photoluminescence (PL) properties of silicon (Si) nanocrystals (NCs) covered with silicon dioxide () are fairly well unraveled; corresponding information for silicon nitride () coverage is scarce. We elucidate important optical and electronic features depending on the embedding dielectric and interface defect (dangling bond, DB) properties. Using density functional theory (DFT) and time‐dependent (TD‐) DFT for ground state (GS) and excited state (ES) properties, respectively, we compute fully ‐ and OH‐covered NCs of 11–26 Å size, enabling comparisons with experimental data. Our non‐radiative Shockley‐Read‐Hall (SRH) recombination model of DBs at NC/dielectric interfaces demonstrates that SRH recombination is substantially higher for ‐covered NCs. An ensemble TD‐DFT calculation of the eight lowest fundamental transitions accurately describes the absorption edge. Exciton binding energies are significantly smaller in ‐ versus ‐covered NCs due to the delocalizing versus self‐localizing impact of the dielectric onto the exciton. We find higher optical absorption rates for ‐embedded NCs versus ‐embedded NCs. However, SRH interface recombination renders the PL of ‐embedded NCs inferior to their ‐embedded counterparts. Finally, we explain a discrepancy in PL gaps of free‐standing oxidized versus ‐embedded NCs by considering adequate phononic boundary conditions.

Designing Direct Z-Scheme Heterojunctions Enabled by Edge-Modified Phosphorene Nanoribbons for Photocatalytic Overall Water Splitting.

Direct Z-scheme photocatalyst possess promising potential to utilize solar radiation for photocatalytic overall water splitting; however, the design and characterization remain challenging. Here, we construct and verify a direct Z-scheme heterojunction using edge-modified phosphorene-nanoribbons (X-PNRs, where X = OH and OCN) with first-principles ground-state and excited-state density functional theory (DFT) calculations. The ground-state calculations provide fundamental properties such as geometric structure and band alignment. The linear-response time-dependent DFT (LR-TDDFT) calculations exhibit the photogenerated charge distribution and demonstrate the generation of interlayer excitons in heterojunctions, which are advantageous to the electron-hole recombination in Z-scheme heterojunctions. The ultrafast charge transfer at the interface studied by time-dependent ab initio nonadiabatic molecular dynamics (NAMD) simulations indicates that interlayer electron-hole recombination is prior to intralayer recombination for the OH/OCN-PNRs heterojunction, showing the characteristics of a Z-scheme heterojunction. Therefore, our computational work provides a universal strategy to design direct Z-scheme heterojunction photocatalysts for overall water splitting.

Information theoretical and thermodynamic view of the excited-state density functional theory of Coulomb systems.

Excited states of Coulomb systems are studied within density functional theory with information theoretical quantities. The Ghosh-Berkowitz-Parr thermodynamic transcription is extended to excited states, and the concept of the local temperature is introduced. It is shown that extremization of information entropy or Fisher information results in a constant temperature. For Coulomb systems, there is a simple relation between the total energy and phase-space Fisher information. The phase-space fidelity between excited states is proportional to the position-space fidelity, with a factor of proportionality depending on total energies. The phase-space relative entropy is equal to the position-space relative entropy plus a term depending only on the total energies. The relationship between the phase-space fidelity susceptibility and Fisher information is also presented.

8-(Pyridin-2-yl)quinolin-7-ol as a Platform for Conjugated Proton Cranes: A DFT Structural Design

Theoretical design of conjugated proton cranes, based on 7-hydroxyquinoline as a tautomeric sub-unit, has been attempted by using ground and excited state density functional theory (DFT) calculations in various environments. The proton crane action request existence of a single enol tautomer in ground state, which under excitation goes to the excited keto tautomer through a series of consecutive excited-state intramolecular proton transfer (ESIPT) steps with the participation of the crane sub-unit. A series of substituted pyridines was used as crane sub-units and the corresponding donor-acceptor interactions were evaluated. The results suggest that the introduction of strong electron donor substituents in the pyridine ring creates optimal conditions for 8-(pyridin-2-yl)quinolin-7-ols to act as proton cranes.

Ultrafast processes in photochromic material YHxOy studied by excited-state density functional theory simulation

Oxygen-containing rare-earth metal hydride, YHxOy, is a newly found photochromic material showing fast photoresponse. While its preparation method, optical properties and structural features have been studied extensively, the photochromic mechanism in YHxOy remains unknown. Here, using excited-state molecular dynamics simulation based on the recently developed real-time time-dependent density functional theory (RT-TDDFT) method, we study the photochemical reactions in YHxOy. We find that under photoexcitation, dihydrogen defects are formed within 100 fs. The dihydrogen defect behaves as a shallow donor and renders the material strongly n-type doped, which could be responsible for the photochromic effect observed in YHxOy. We also find that oxygen concentration affects the metastability of the dihydrogen species, meaning that the energy barrier for the dihydrogen to dissociate is related to the oxygen concentration. The highest barrier of 0.28 eV is found in our model with O/Y=1:8. If the oxygen concentration is too low, the dihydrogen will quickly dissociate when the excitation is turned off. If the oxygen concentration is too high, the dihydrogen dissociates even when the excitation is still on.

Environment-Sensitive Azepane-Substituted β-Diketones and Difluoroboron Complexes with Restricted C–C Bond Rotation

Luminescent β-diketones (bdks) and difluoroboron coordinated complexes (BF₂bdks) exhibit many environment-sensitive properties, such as solvatochromism, viscochromism, aggregation-induced emission (AIE), and thermal and mechanochromic luminescence (ML). In a previous study, an azepane-substituted bdk ligand (L1) and boron dye (D1) showed noteworthy luminescence properties but low quantum yields (Φ, L1: 0.26; D1: 0.02) due to free intramolecular bond rotation and twisted intramolecular charge transfer state formation with associated nonradiative decay. Thus, in order to improve the quantum yields, an azepane-substituted bdk ligand (L2) and boron complex (D2) with restricted C–C bond rotation were synthesized, and various luminescence properties were investigated. Restricting bond rotation blue-shifted absorptions and emissions, increased lifetimes, and greatly improved quantum yields (Φ, L2: 0.47; D2: 0.83). Excited state density functional theory calculations displayed twisted geometries for L1 and D1 but more planar geometries for L2 and D2. All compounds showed red-shifted emissions in more polar solvents. For viscochromism, L1 and D1 exhibited higher emission intensity in more viscous media. However, L2 and D2 did not show dramatic viscochromism, substantiating the relation between viscosity sensitivity and intramolecular bond twisting. Additionally, while both ligands showed quenched emission upon aggregation, the dyes exhibited AIE regardless of bond restriction. Thermal and ML studies showed a more dramatic emission shift for L2 than L1 between thermally annealed and melt-quenched states. In summary, the quantum yields of the azepane-substituted bdk ligand and boron dye were successfully improved by restricting the intramolecular C–C bond rotation, making various luminescence properties more promising for environment-sensitive applications.

Electron correlations in an excited state of a quantum dot in a uniform magnetic field

Electron correlations in a two-electron two-dimensional ‘artificial atom’ or quantum dot (with harmonic confining potential) in the presence of a uniform magnetic field in an excited singlet state are studied via quantal density functional theory (QDFT). QDFT allows for the separation of the electron correlations due to the Pauli exclusion principle and Coulomb repulsion, as well as the determination of the contribution of these correlations to the kinetic energy. The QDFT mapping is from the excited state of the quantum dot to one of noninteracting fermions in their ground state possessing the same basic variables of the density and physical current density, and the same orbital and spin angular momentum. A detailed analysis of these correlations in terms of their quantal sources, the corresponding ‘classical’ fields, and resulting potentials and energies is presented. The key conclusions are that as in natural atoms, the contributions of the Pauli and Coulomb correlations relative to the total energy for the excited state, are less than but of the same order of magnitude as those for the ground state of a quantum dot. However, in contrast, the correlation-kinetic contributions are an order of magnitude greater than those for a quantum dot in its ground state. These correlations constitute nearly 75% of the kinetic and 25% of the total energy. This result is consistent with prior work on low electron density Wigner systems in three-dimensions in which correlation-kinetic effects too play a significant role. The significance of these correlations to traditional excited state density functional theory is noted.

Luminescent Re(I) Carbonyl Complexes as Trackable PhotoCORMs for CO delivery to Cellular Targets.

A family of Re(I) carbonyl complexes of general formula [ReX(CO)3(phen)]0/1+ (where X = Cl-, CF3SO3-, MeCN, PPh3, and methylimidazole) derived from 1,10-phenanthroline (phen) exhibits variable emission characteristics depending on the presence of the sixth ancillary ligand/group (X). All complexes but with X = MeCN exhibit moderate CO release upon irradiation with low-power UV light and are indefinitely stable in anaerobic/aerobic environment in solution as well as in solid state when kept under dark condition. These CO donors liberate three, one, or no CO depending on the nature of sixth ligand upon illumination as studied with the aid of time-dependent IR spectroscopy. Results of excited-state density functional theory (DFT) and time-dependent DFT calculations provided insight into the origin of the emission characteristics of these complexes. The luminescent rheinum(I) photoCORMs uniformly displayed efficient cellular internalization by the human breast adenocarcinoma cells, MDA-MB-231, while the complex with PPh3 as ancillary ligand showed moderate nuclear localization in addition to the cytosolic distribution. These species hold significant promise as theranostic photoCORMs (photoinduced CO releasing molecules), where the entry of the pro-drug can be tracked within the cellular matrices.

Theoretical rationalization for reduced charge recombination in bulky carbazole-based sensitizers in solar cells.

The search for greater efficiency in organic dye-sensitized solar cells (DSCs) and in their perovskite cousins is greatly aided by a more complete understanding of the spectral and morphological properties of the photoactive layer. This investigation resolves a discrepancy in the observed photoconversion efficiency (PCE) of two closely related DSCs based on carbazole-containing D-π-A organic sensitizers. Detailed theoretical characterization of the absorption spectra, dye adsorption on TiO2 , and electronic couplings for charge separation and recombination permit a systematic determination of the origin of the difference in PCE. Although the two dyes produce similar spectral features, ground- and excited-state density functional theory (DFT) simulations reveal that the dye with the bulkier donor group adsorbs more strongly to TiO2 , experiences limited π-π aggregation, and is more resistant to loss of excitation energy via charge recombination on the dye. The effects of conformational flexibility on absorption spectra and on the electronic coupling between the bright exciton and charge-transfer states are revealed to be substantial and are characterized through density-functional tight-binding (DFTB) molecular dynamics sampling. These simulations offer a mechanistic explanation for the superior open-circuit voltage and short-circuit current of the bulky-donor dye sensitizer and provide theoretical justification of an important design feature for the pursuit of greater photocurrent efficiency in DSCs. © 2017 Wiley Periodicals, Inc.

How Parallel Are Excited State Potential Energy Surfaces from Time-Independent and Time-Dependent DFT? A BODIPY Dye Case Study

To support the development and characterization of chromophores with targeted photophysical properties, excited-state electronic structure calculations should rapidly and accurately predict how derivatization of a chromophore will affect its excitation and emission energies. This paper examines whether a time-independent excited-state density functional theory (DFT) approach meets this need through a case study of BODIPY chromophore photophysics. A restricted open-shell Kohn-Sham (ROKS) treatment of the S1 excited state of BODIPY dyes is contrasted with linear-response time-dependent density functional theory (TDDFT). Vertical excitation energies predicted by the two approaches are remarkably different due to overestimation by TDDFT and underestimation by ROKS relative to experiment. Overall, ROKS with a standard hybrid functional provides the more accurate description of the S1 excited state of BODIPY dyes, but excitation energies computed by the two methods are strongly correlated. The two approaches also make similar predictions of shifts in the excitation energy upon functionalization of the chromophore. TDDFT and ROKS models of the S1 potential energy surface are then examined in detail for a representative BODIPY dye through molecular dynamics sampling on both model surfaces. We identify the most significant differences in the sampled surfaces and analyze these differences along selected normal modes. Differences between ROKS and TDDFT descriptions of the S1 potential energy surface for this BODIPY derivative highlight the continuing need for validation of widely used approximations in excited state DFT through experimental benchmarking and comparison to ab initio reference data.

Ghost-interaction correction in ensemble density-functional theory for excited states with and without range separation

Ensemble density-functional theory (eDFT) suffers from the so-called "ghost interaction" error when approximate exchange-correlation functionals are used. In this work, we present a rigorous ghost interaction correction (GIC) scheme in the context of range-separated eDFT. The method relies on an exact decomposition of the ensemble short-range exchange-correlation energy into a multideterminantal exact exchange term, which involves the long-range interacting ensemble density matrix instead of the Kohn--Sham (KS) one, and a complementary density-functional correlation energy. A generalized adiabatic connection formula is derived for the latter. In order to perform practical calculations, the complementary correlation functional has been simply modeled by its ground-state local density approximation (LDA) while long-range interacting ground- and excited-state wavefunctions have been obtained self-consistently by combining a long-range configuration interaction calculation with a short-range LDA potential. We show that GIC reduces the curvature of approximate range-separated ensemble energies drastically while providing considerably more accurate excitation energies, even for charge-transfer and double excitations. Interestingly, the method performs well also in the context of standard KS-eDFT, which is recovered when the range-separation parameter is set to zero.

Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H2 molecule

A generalised adiabatic connection for ensembles (GACE) is presented. In contrast to the traditional adiabatic connection formulation, both ensemble weights and interaction strength can vary along a GACE path while the ensemble density is held fixed. The theory is presented for non-degenerate two-state ensembles but it can in principle be extended to any ensemble of fractionally occupied excited states. Within such a formalism an exact expression for the ensemble exchange–correlation density-functional energy, in terms of the conventional ground-state exchange–correlation energy, is obtained by integration over the ensemble weight. Stringent constraints on the functional are thus obtained when expanding the ensemble exchange–correlation energy through second order in the ensemble weight. For illustration purposes, the analytical derivation of the GACE is presented for the H2 model system in a minimal basis, leading thus to a simple density-functional approximation to the ensemble exchange–correlation energy. Encouraging results were obtained with this approximation for the description in a large basis of the first 1Σ+g excitation in H2 upon bond stretching. Finally, a range-dependent GACE has been derived, providing thus a pathway to the development of a rigorous state-average multi-determinant density-functional theory.

Excited-state density functional theory

Starting with a brief introduction to excited-state density functional theory, we present our method of constructing modified local density approximated (MLDA) energy functionals for the excited states. We show that these functionals give accurate results for kinetic energy and exchange energy compared to the ground state LDA functionals. Further, with the inclusion of GGA correction, highly accurate total energies for excited states are obtained. We conclude with a brief discussion on the further direction of research that include the construction of correlation energy functional and exchange potential for excited states.

Computational Studies of CO2 Activation via Photochemical Reactions with Reduced Sulfur Compounds

Reactions between CO(2) and reduced sulfur compounds (RSC), H(2)S and CH(3)SH, were investigated using ground and excited state density functional theory (DFT) and coupled cluster (CC) methods to explore possible RSC oxidation mechanisms and CO(2) activation mechanisms in the atmospheric environment. Ground electronic state calculations at the CR-CC(2,3)/6-311+G(2df,2p)//CAM-B3LYP/6-311+G(2df,2p) level show proton transfer as a limiting step in the reduction of CO(2) with activation energies of 49.64 and 47.70 kcal/mol, respectively, for H(2)S and CH(3)SH. On the first excited state surface, CR-EOMCC(2,3)/6-311+G(2df,2p)//CAM-B3LYP/6-311+G(2df,2p) calculations reveal that energies of <250 nm are needed to form H(2)S-CO(2) and CH(3)SH-CO(2) complexes allowing facile hydrogen atom transfer. Once excited, all reaction intermediates and transition states are downhill energetically showing either C-H or C-S bond formation in the excited state whereas only C-S bond formation was found in the ground state. Environmental implications of these data are discussed with a focus on tropospheric reactions between CO(2) and RSC, as well as potential for carbon sequestration using photocatalysis.

Time-independent density-functional theory for excited states of Coulomb systems

A Coulomb density is special because it determines not only its Hamiltonian but the degree of excitation as well. We derive Euler equations for excited-state energies and densities that depend only on the electron density. Unlike existing formulations, additional functions and indices are not required; with these functionals, the equations of excited-state density functional theory strongly resemble those of ground-state theory. A critical analysis of the new functionals is included.