Reference Energies for Double Excitations: Improvement and Extension.

In the realm of photochemistry, the significance of double excitations (also known as doubly excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions essential in light-induced chemical reactions as well as their challenging nature from the computational theoretical chemistry point of view. Based on state-of-the-art electronic structure methods (such as high-order coupled-cluster, selected configuration interaction, and multiconfigurational methods), we improve and expand our prior set of accurate reference excitation energies for electronic states exhibiting a substantial amount of double excitations [Loos et al. J. Chem. Theory Comput. 2019, 15, 1939]. This extended collection encompasses 47 electronic transitions across 26 molecular systems that we separate into two distinct subsets: (i) 28 "genuine" doubly excited states where the transitions almost exclusively involve doubly excited configurations and (ii) 19 "partial" doubly excited states which exhibit a more balanced character between singly and doubly excited configurations. For each subset, we assess the performance of high-order coupled-cluster (CC3, CCSDT, CC4, and CCSDTQ) and multiconfigurational methods (CASPT2, CASPT3, PC-NEVPT2, and SC-NEVPT2). Using as a probe the percentage of single excitations involved in a given transition (%T1) computed at the CC3 level, we also propose a simple correction that reduces the errors of CC3 by a factor of 3, for both sets of excitations. We hope that this more complete and diverse compilation of double excitations will help future developments of electronic excited-state methodologies.

State-Specific Coupled-Cluster Methods for Excited States.

We reexamine ΔCCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient when dealing with doubly excited states, a domain in which the standard equation-of-motion CCSD (EOM-CCSD) formalism falls short. Our goal here to evaluate the effectiveness of ΔCCSD when applied to other types of excited states, comparing its consistency and accuracy with EOM-CCSD. To this end, we report a benchmark on excitation energies computed with the ΔCCSD and EOM-CCSD methods for a set of molecular excited-state energies that encompasses not only doubly excited states but also doublet-doublet transitions and (singlet and triplet) singly excited states of closed-shell systems. In the latter case, we rely on a minimalist version of multireference CC known as the two-determinant CCSD method to compute the excited states. Our data set, consisting of 276 excited states stemming from the quest database [Véril et al., WIREs Comput. Mol. Sci. 2021, 11, e1517], provides a significant base to draw general conclusions concerning the accuracy of ΔCCSD. Except for the doubly excited states, we found that ΔCCSD underperforms EOM-CCSD. For doublet-doublet transitions, the difference between the mean absolute errors (MAEs) of the two methodologies (of 0.10 and 0.07 eV) is less pronounced than that obtained for singly excited states of closed-shell systems (MAEs of 0.15 and 0.08 eV). This discrepancy is largely attributed to a greater number of excited states in the latter set exhibiting multiconfigurational characters, which are more challenging for ΔCCSD. We also found typically small improvements by employing state-specific optimized orbitals.

Reference Energies for Valence Ionizations and Satellite Transitions.

Upon ionization of an atom or a molecule, another electron (or more) can be simultaneously excited. These concurrently generated states are called "satellites" (or shakeup transitions) as they appear in ionization spectra as higher-energy peaks with weaker intensity and larger width than the main peaks associated with single-particle ionizations. Satellites, which correspond to electronically excited states of the cationic species, are notoriously challenging to model using conventional single-reference methods due to their high excitation degree compared to the neutral reference state. This work reports 42 satellite transition energies and 58 valence ionization potentials (IPs) of full configuration interaction quality computed in small molecular systems. Following the protocol developed for the quest database [Véril, M.; Scemama, A.; Caffarel, M.; Lipparini, F.; Boggio-Pasqua, M.; Jacquemin, D.; and Loos, P.-F. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2021, 11, e1517], these reference energies are computed using the configuration interaction using a perturbative selection made iteratively (CIPSI) method. In addition, the accuracy of the well-known coupled-cluster (CC) hierarchy (CC2, CCSD, CC3, CCSDT, CC4, and CCSDTQ) is gauged against these new accurate references. The performances of various approximations based on many-body Green's functions (GW, GF2, and T-matrix) for IPs are also analyzed. Their limitations in correctly modeling satellite transitions are discussed.

A mountaineering strategy to excited states: Accurate vertical transition energies and benchmarks for substituted benzenes.

In an effort to expand the existing QUEST database of accurate vertical transition energies [Véril et al. WIREs Comput. Mol. Sci. 2021, 11, e1517], we have modeled more than 100 electronic excited states of different natures (local, charge-transfer, Rydberg, singlet, and triplet) in a dozen of mono- and di-substituted benzenes, including aniline, benzonitrile, chlorobenzene, fluorobenzene, nitrobenzene, among others. To establish theoretical best estimates for these vertical excitation energies, we have employed advanced coupled-cluster methods including iterative triples (CC3 and CCSDT) and, when technically possible, iterative quadruples (CC4). These high-level computational approaches provide a robust foundation for benchmarking a series of popular wave function methods. The evaluated methods all include contributions from double excitations (ADC(2), CC2, CCSD, CIS(D), EOM-MP2, STEOM-CCSD), along with schemes that also incorporate perturbative or iterative triples (ADC(3), CCSDR(3), CCSD(T)(a) ⋆ $$ {}^{\star } $$ , and CCSDT-3). This systematic exploration not only broadens the scope of the QUEST database but also facilitates a rigorous assessment of different theoretical approaches in the framework of a homologous chemical series, offering valuable insights into the accuracy and reliability of these methods in such cases. We found that both ADC(2.5) and CCSDT-3 can provide very consistent estimates, whereas among less expensive methods SCS-CC2 is likely the most effective approach. Importantly, we show that some lower order methods may offer reasonable trends in the homologous series while providing quite large average errors, and vice versa. Consequently, benchmarking the accuracy of a model based solely on absolute transition energies may not be meaningful for applications involving a series of similar compounds.

Can GW handle multireference systems?

Due to the infinite summation of bubble diagrams, the GW approximation of Green's function perturbation theory has proven particularly effective in the weak correlation regime, where this family of Feynman diagrams is important. However, the performance of GW in multireference molecular systems, characterized by strong electron correlation, remains relatively unexplored. In the present study, we investigate the ability of GW to handle closed-shell multireference systems in their singlet ground state by examining four paradigmatic scenarios. First, we analyze a prototypical example of a chemical reaction involving strong correlation: the potential energy curve of BeH2 during the insertion of a beryllium atom into a hydrogen molecule. Second, we compute the electron detachment and attachment energies of a set of molecules that exhibit a variable degree of multireference character at their respective equilibrium geometries: LiF, BeO, BN, C2, B2, and O3. Third, we consider a H6 cluster with a triangular arrangement, which features a notable degree of spin frustration. Finally, the dissociation curve of the HF molecule is studied as an example of single bond breaking. These investigations highlight a nuanced perspective on the performance of GW for strong correlation depending on the level of self-consistency, the choice of initial guess, and the presence of spin-symmetry breaking at the Hartree-Fock level.

Rationale for the extrapolation procedure in selected configuration interaction.

Selected configuration interaction (SCI) methods have emerged as state-of-the-art methodologies for achieving high accuracy and generating benchmark reference data for ground and excited states in small molecular systems. However, their precision relies heavily on extrapolation procedures to produce a final estimate of the exact result. Using the structure of the exact electronic energy landscape, we provide a rationale for the common linear extrapolation of the variational energy as a function of the second-order perturbative correction. In particular, we demonstrate that the energy gap and the coupling between the so-called internal and external spaces are the key factors determining the rate at which the linear regime is reached. Starting from the first principles, we also derive a new non-linear extrapolation formula that improves the post-processing of data generated from SCI methods and can be applied to both ground- and excited-state energies.

Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet-Triplet Gap.

Molecules that violate Hund's rule and exhibit an inverted gap between the lowest singlet S1 and triplet T1 excited states have attracted considerable attention due to their potential applications in optoelectronics. Among these molecules, the triangular-shaped heptazine, and its derivatives, have been in the limelight. However, conflicting reports have arisen regarding the relative energies of S1 and T1. Here, we employ highly accurate levels of theory, such as CC3, to not only resolve the debate concerning the sign but also quantify the magnitude of the S1-T1 gap. We also determined the 0-0 energies to evaluate the significance of the vertical approximation. In addition, we compute reference S1-T1 gaps for a series of 10 related molecules. This enables us to benchmark lower-order methods for future applications in larger systems within the same family of compounds. This contribution can serve as a foundation for the design of triangular-shaped molecules with enhanced photophysical properties.

Seniority and Hierarchy Configuration Interaction for Radicals and Excited States.

Hierarchy configuration interaction (hCI) has recently been introduced as an alternative configuration interaction (CI) route combining excitation degree and seniority number and has been shown to efficiently recover both dynamic and static correlations for closed-shell molecular systems [ J. Phys. Chem. Lett. 2022, 13, 4342]. Here we generalize hCI for an arbitrary reference determinant, allowing calculations for radicals and excited states in a state-specific way. We gauge this route against excitation-based CI (eCI) and seniority-based CI (sCI) by evaluating how different ground-state properties of radicals converge to the full CI limit. We find that hCI outperforms or matches eCI, whereas sCI is far less accurate, in line with previous observations for closed-shell molecules. Employing second-order Epstein-Nesbet (EN2) perturbation theory as a correction significantly accelerates the convergence of hCI and eCI. We further explore various hCI and sCI models to calculate the excitation energies of closed- and open-shell systems. Our results underline that the choice of both the reference determinant and the set of orbitals drives the fine balance between correlation of ground and excited states. State-specific hCI2 and higher-order models perform similarly to their eCI counterparts, whereas lower orders of hCI deliver poor results unless supplemented by the EN2 correction, which substantially improves their accuracy. In turn, sCI1 produces decent excitation energies for radicals, encouraging the development of related seniority-based coupled-cluster methods.

Reference Vertical Excitation Energies for Transition Metal Compounds.

To enrich and enhance the diversity of the quest database of highly accurate excitation energies [Véril, M.; et al. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2021, 11, e1517], we report vertical transition energies in transition metal compounds. Eleven diatomic molecules with a singlet or doublet ground state containing a fourth-row transition metal (CuCl, CuF, CuH, ScF, ScH, ScO, ScS, TiN, ZnH, ZnO, and ZnS) are considered, and the corresponding excitation energies are computed using high-level coupled-cluster (CC) methods, namely, CC3, CCSDT, CC4, and CCSDTQ, as well as multiconfigurational methods such as CASPT2 and NEVPT2. In many cases, to provide more comprehensive benchmark data, we also provide full configuration interaction estimates computed with the configuration interaction using a perturbative selection made iteratively (CIPSI) method. Based on these calculations, theoretical best estimates of the transition energies are established in both the aug-cc-pVDZ and aug-cc-pVTZ basis sets. This allows us to accurately assess the performance of the CC and multiconfigurational methods for this specific set of challenging transitions. Furthermore, comparisons with experimental data and previous theoretical results are also reported.

The three channels of many-body perturbation theory: GW, particle-particle, and electron-hole T-matrix self-energies.

We derive the explicit expression of the three self-energies that one encounters in many-body perturbation theory: the well-known GW self-energy, as well as the particle-particle and electron-hole T-matrix self-energies. Each of these can be easily computed via the eigenvalues and eigenvectors of a different random-phase approximation linear eigenvalue problem that completely defines their corresponding response function. For illustrative and comparative purposes, we report the principal ionization potentials of a set of small molecules computed at each level of theory. The performance of these schemes on strongly correlated systems (B2 and C2) is also discussed.

Exact Excited-State Functionals of the Asymmetric Hubbard Dimer.

The exact functionals associated with the (singlet) ground state and the two singlet excited states of the asymmetric Hubbard dimer at half-filling are calculated using both Levy's constrained search and Lieb's convex formulation. While the ground-state functional is, as is commonly known, a convex function with respect to the density, the functional associated with the doubly excited state is found to be concave. Also, because the density-potential mapping associated with the first excited state is noninvertible, its "functional" is a partial, multivalued function composed of one concave and one convex branch that correspond to two separate domains of the external potential. Remarkably, it is found that, although the one-to-one mapping between density and external potential may not apply (as in the case of the first excited state), each state-specific energy and corresponding universal functional are "functions" whose derivatives are each other's inverse, just as in the ground state formalism.

Connections and performances of Green's function methods for charged and neutral excitations.

In recent years, Green's function methods have garnered considerable interest due to their ability to target both charged and neutral excitations. Among them, the well-established GW approximation provides accurate ionization potentials and electron affinities and can be extended to neutral excitations using the Bethe-Salpeter equation (BSE) formalism. Here, we investigate the connections between various Green's function methods and evaluate their performance for charged and neutral excitations. Comparisons with other widely known second-order wave function methods are also reported. Additionally, we calculate the singlet-triplet gap of cycl[3,3,3]azine, a model molecular emitter for thermally activated delayed fluorescence, which has the particularity of having an inverted gap thanks to a substantial contribution from the double excitations. We demonstrate that, within the GW approximation, a second-order BSE kernel with dynamical correction is required to predict this distinctive characteristic.

A Similarity Renormalization Group Approach to Green's Function Methods.

The family of Green's function methods based on the GW approximation has gained popularity in the electronic structure theory thanks to its accuracy in weakly correlated systems combined with its cost-effectiveness. Despite this, self-consistent versions still pose challenges in terms of convergence. A recent study [Monino and Loos J. Chem. Phys. 2022, 156, 231101.] has linked these convergence issues to the intruder-state problem. In this work, a perturbative analysis of the similarity renormalization group (SRG) approach is performed on Green's function methods. The SRG formalism enables us to derive, from first-principles, the expression of a naturally static and Hermitian form of the self-energy that can be employed in quasiparticle self-consistent GW (qsGW) calculations. The resulting SRG-based regularized self-energy significantly accelerates the convergence of qsGW calculations, slightly improves the overall accuracy, and is straightforward to implement in existing code.

State-Specific Configuration Interaction for Excited States.

We introduce and benchmark a systematically improvable route for excited-state calculations, labeled state-specific configuration interaction (ΔCI), which is a particular realization of multiconfigurational self-consistent field and multireference configuration interaction. Starting with a reference built from optimized configuration state functions, separate CI calculations are performed for each targeted state (hence, state-specific orbitals and determinants). Accounting for single and double excitations produces the ΔCISD model, which can be improved with second-order Epstein-Nesbet perturbation theory (ΔCISD+EN2) or a posteriori Davidson corrections (ΔCISD+Q). These models were gauged against a vast and diverse set of 294 reference excitation energies. We have found that ΔCI is significantly more accurate than standard ground-state-based CI, whereas close performances were found between ΔCISD and EOM-CC2 and between ΔCISD+EN2 and EOM-CCSD. For larger systems, ΔCISD+Q delivers more accurate results than EOM-CC2 and EOM-CCSD. The ΔCI route can handle challenging multireference problems, singly and doubly excited states, from closed- and open-shell species, with overall comparable accuracy and thus represents a promising alternative to more established methodologies. In its current form, however, it is reliable only for relatively low-lying excited states.

Ground- and Excited-State Dipole Moments and Oscillator Strengths of Full Configuration Interaction Quality.

We report ground- and excited-state dipole moments and oscillator strengths (computed in different "gauges" or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as Configuration Interaction using a Perturbative Selection made Iteratively (CIPSI). Thanks to a set encompassing 35 ground- and excited-state properties computed in 11 small molecules, the present near-FCI estimates allow us to assess the accuracy of high-order coupled-cluster (CC) calculations including up to quadruple excitations. In particular, we show that incrementing the excitation degree of the CC expansion (from CC with singles and doubles (CCSD) to CC with singles, doubles, and triples (CCSDT) or from CCSDT to CC with singles, doubles, triples, and quadruples (CCSDTQ)) reduces the average error with respect to the near-FCI reference values by approximately 1 order of magnitude.

Connections between many-body perturbation and coupled-cluster theories.

Here, we build on the works of Scuseria et al. [J. Chem. Phys. 129, 231101 (2008)] and Berkelbach [J. Chem. Phys. 149, 041103 (2018)] to show connections between the Bethe-Salpeter equation (BSE) formalism combined with the GW approximation from many-body perturbation theory and coupled-cluster (CC) theory at the ground- and excited-state levels. In particular, we show how to recast the GW and Bethe-Salpeter equations as non-linear CC-like equations. Similitudes between BSE@GW and the similarity-transformed equation-of-motion CC method are also put forward. The present work allows us to easily transfer key developments and the general knowledge gathered in CC theory to many-body perturbation theory. In particular, it may provide a path for the computation of ground- and excited-state properties (such as nuclear gradients) within the GW and BSE frameworks.

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science.

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 exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.

Benchmarking CASPT3 vertical excitation energies.

Based on 280 reference vertical transition energies of various excited states (singlet, triplet, valence, Rydberg, n → π*, π → π*, and double excitations) extracted from the QUEST database, we assess the accuracy of complete-active-space third-order perturbation theory (CASPT3), in the context of molecular excited states. When one applies the disputable ionization-potential-electron-affinity (IPEA) shift, we show that CASPT3 provides a similar accuracy as its second-order counterpart, CASPT2, with the same mean absolute error of 0.11 eV. However, as already reported, we also observe that the accuracy of CASPT3 is almost insensitive to the IPEA shift, irrespective of the transition type and system size, with a small reduction in the mean absolute error to 0.09 eV when the IPEA shift is switched off.

Reference Energies for Cyclobutadiene: Automerization and Excited States.

Cyclobutadiene is a well-known playground for theoretical chemists and is particularly suitable to test ground- and excited-state methods. Indeed, due to its high spatial symmetry, especially at the D4h square geometry but also in the D2h rectangular arrangement, the ground and excited states of cyclobutadiene exhibit multiconfigurational characters and single-reference methods, such as standard adiabatic time-dependent density-functional theory (TD-DFT) or standard equation-of-motion coupled cluster (EOM-CC), are notoriously known to struggle in such situations. In this work, using a large panel of methods and basis sets, we provide an extensive computational study of the automerization barrier (defined as the difference between the square and rectangular ground-state energies) and the vertical excitation energies at D2h and D4h equilibrium structures. In particular, selected configuration interaction (SCI), multireference perturbation theory (CASSCF, CASPT2, and NEVPT2), and coupled-cluster (CCSD, CC3, CCSDT, CC4, and CCSDTQ) calculations are performed. The spin-flip formalism, which is known to provide a qualitatively correct description of these diradical states, is also tested within TD-DFT (combined with numerous exchange-correlation functionals) and the algebraic diagrammatic construction [ADC(2)-s, ADC(2)-x, and ADC(3)]. A theoretical best estimate is defined for the automerization barrier and for each vertical transition energy.

Unphysical discontinuities, intruder states and regularization in GW methods.

By recasting the non-linear frequency-dependent GW quasiparticle equation into a linear eigenvalue problem, we explain the appearance of multiple solutions and unphysical discontinuities in various physical quantities computed within the GW approximation. Considering the GW self-energy as an effective Hamiltonian, it is shown that these issues are key signatures of strong correlation in the (N ± 1)-electron states and can be directly related to the intruder state problem. A simple and efficient regularization procedure inspired by the similarity renormalization group is proposed to avoid such issues and speed up the convergence of partially self-consistent GW calculations.