Coupled Cluster Singles And Doubles Research Articles

Quantum Mechanical Versus Polarizable Embedding Schemes: A Study of the Xray Absorption Spectra of Aqueous Ammonia and Ammonium.

The X-ray absorption spectra of aqueous ammonia and ammonium are computed using a combination of coupled cluster singles and doubles (CCSD) with different quantum mechanical and molecular mechanical embedding schemes. Specifically, we compare frozen Hartree-Fock (HF) density embedding, polarizable embedding (PE), and polarizable density embedding (PDE). Integrating CCSD with frozen HF density embedding is possible within the CC-in-HF framework, which circumvents the conventional system-size limitations of standard coupled cluster methods. We reveal similarities between PDE and frozen HF density descriptions, while PE spectra differ significantly. By including approximate triple excitations, we also investigate the effect of improving the electronic structure theory. The spectra computed using this approach show an improved intensity ratio compared to CCSD-in-HF. Charge transfer analysis of the excitations shows the local character of the pre-edge and main-edge, while the post-edge is formed by excitations delocalized over the first solvation shell and beyond.

Cluster perturbation theory IX: Perturbation series for the coupled cluster singles and doubles ground state energy.

In this paper, we develop and analyze a number of perturbation series that target the coupled cluster singles and doubles (CCSD) ground state energy. We show how classical Møller-Plesset perturbation theory series can be restructured to target the CCSD energy based on a reference CCS calculation and how the corresponding cluster perturbation series differs from the classical Møller-Plesset perturbation series. Subsequently, we reformulate these series using the coupled cluster Lagrangian framework to obtain series, where fourth and fifth order energies are determined only using parameters through second order. To test the methods, we perform a series of test calculations on molecular photoswitches of both total energies and reaction energies. We find that the fifth order reaction energies are of CCSD quality and that they are of comparable accuracy to state-of-the-art approximations to the CCSD energy based on local pair natural orbitals. The advantage of the present approach over local correlation methods is the absence of user defined threshold parameters for neglecting or approximating contributions to the correlation energy. Fixed threshold parameters lead to discontinuous energy surfaces, although this effect is often small enough to be ignored, but the present approach has a differentiable energy that will facilitate derivation and implementation of gradients and higher derivatives. A further advantage is that the calculation of the perturbation correction is non-iterative and can, therefore, be calculated in parallel, leading to a short time-to-solution.

Exploring Alternate Methods for the Calculation of High-Level Vibrational Corrections of NMR Spin-Spin Coupling Constants.

Traditional nuclear magnetic resonance (NMR) calculations typically treat systems with a Born-Oppenheimer-derived electronic wave function that is solved for a fixed nuclear geometry. One can numerically account for this neglected nuclear motion by averaging over property values for all nuclear geometries with a vibrational wave function and adding this expectation value as a correction to an equilibrium geometry property value. Presented are benchmark coupled-cluster singles and doubles (CCSD) vibrational corrections to spin-spin coupling constants (SSCCs) computed at the level of vibrational second-order perturbation theory (VPT2) using the vibrational averaging driver of the CFOUR program. As CCSD calculations of vibrational corrections are very costly, cheaper electronic structure methods are explored via a newly developed Python vibrational averaging program within the Dalton Project. Namely, results obtained with the second-order polarization propagator approximation (SOPPA) and density functional theory (DFT) with the B3LYP and PBE0 exchange-correlation functionals are compared to the benchmark CCSD//CCSD(T) and experimental values. CCSD//CCSD(T) corrections are also combined with literature CC3 equilibrium geometry values to form the highest-order vibrationally corrected values available (i.e., CC3//CCSD(T) + CCSD//CCSD(T)). CCSD//CCSD(T) statistics showed favorable statistics in comparison to experimental values, albeit at an unfavorably high computational cost. A cheaper CCSD//CCSD(T) + B3LYP method showed quite similar mean absolute deviation (MAD) values as CCSD//CCSD(T), concluding that CCSD//CCSD(T) + B3LYP is optimal in terms of cost and accuracy. With reference to experimental values, a vibrational correction was not worth the cost for all of the other methods tested. Finally, deviation statistics showed that CC3//CCSD(T) + CCSD//CCSD(T) vibrational-corrected equilibrium values deteriorated in comparison to CCSD//CCSD(T) attributed to the use of a smaller basis set or lack of solvation effects for the CC3 equilibrium calculations.

Capturing the electron-electron cusp with the coupling-constant averaged exchange-correlation hole: A case study for Hooke's atoms.

In density-functional theory, the exchange-correlation (XC) energy can be defined exactly through the coupling-constant (λ) averaged XC hole n̄xc(r,r'), representing the probability depletion of finding an electron at r' due to an electron at r. Accurate knowledge of n̄xc(r,r') has been crucial for developing XC energy density-functional approximations and understanding their performance for molecules and materials. However, there are very few systems for which accurate XC holes have been calculated since this requires evaluating the one- and two-particle reduced density matrices for a reference wave function over a range of λ while the electron density remains fixed at the physical (λ = 1) density. Although the coupled-cluster singles and doubles (CCSD) method can yield exact results for a two-electron system in the complete basis set limit, it cannot capture the electron-electron cusp using finite basis sets. Focusing on Hooke's atom as a two-electron model system for which certain analytic solutions are known, we examine the effect of this cusp error on the XC hole calculated using CCSD. The Lieb functional is calculated at a range of coupling constants to determine the λ-integrated XC hole. Our results indicate that, for Hooke's atoms, the error introduced by the description of the electron-electron cusp using Gaussian basis sets at the CCSD level is negligible compared to the basis set incompleteness error. The system-, angle-, and coupling-constant-averaged XC holes are also calculated and provide a benchmark against which the Perdew-Burke-Ernzerhof and local density approximation XC hole models are assessed.

Cluster-in-Molecule Approach with Explicitly Correlated Methods for Large Molecules.

In this article, we present a series of explicitly correlated local correlation methods developed under the cluster-in-molecule (CIM) framework, including explicitly correlated second-order Møller-Plesset perturbation (MP2), coupled-cluster singles and doubles (CCSD), domain-based local pair natural orbital CCSD (DLPNO-CCSD), and DLPNO-CCSD with perturbative triples (DLPNO-CCSD(T)). In these methods, F12 correction is decomposed into contributions from each occupied local molecular orbital and then evaluated independently in a given cluster, which consists of a subset of localized orbitals. These newly developed methods allow F12 calculations of large molecules (up to 145 atoms for quasi-one-dimensional systems) on a single node. We use these methods to investigate the relative stability between extended and folded alkane C30H62, the relative stability of four secondary structures of a polyglycine Ace(Gly)10NH2, and the binding energies of two host-guest complexes. The results demonstrate that the combination of CIM with F12 methods is a promising way to investigate large molecules with small basis set errors.

Analytical Second-Order Properties for the Random Phase Approximation: Nuclear Magnetic Resonance Shieldings.

A method for the analytical computation of nuclear magnetic resonance (NMR) shieldings within the direct random phase approximation (RPA) is presented. As a starting point, we use the RPA ground-state energy expression within the resolution-of-the-identity approximation in the atomic-orbital formalism. As has been shown in a recent benchmark study using numerical second derivatives [Glasbrenner, M. J. Chem. Theory Comput. 2022, 18, 192], RPA based on a Hartree-Fock reference shows accuracies comparable to coupled cluster singles and doubles (CCSD) for NMR chemical shieldings. Together with the much lower computational cost of RPA, it has emerged as an accurate method for the computation of NMR shieldings. Therefore, we aim to extend the applicability of RPA NMR to larger systems by introducing analytical second-order derivatives, making it a viable method for the accurate and efficient computation of NMR chemical shieldings.

Quantum simulation of preferred tautomeric state prediction

Prediction of tautomers plays an essential role in computer-aided drug discovery. However, it remains a challenging task nowadays to accurately predict the canonical tautomeric form of a given drug-like molecule. Lack of extensive tautomer databases, most likely due to the difficulty in experimental studies, hampers the development of effective empirical methods for tautomer predictions. A more accurate estimation of the stable tautomeric form can be achieved by quantum chemistry calculations. Yet, the computational cost required prevents quantum chemistry calculation as a standard tool for tautomer prediction in computer-aided drug discovery. In this paper we propose a hybrid quantum chemistry-quantum computation workflow to efficiently predict the dominant tautomeric form. Specifically, we select active-space molecular orbitals based on quantum chemistry methods. Then we utilize efficient encoding methods to map the Hamiltonian onto quantum devices to reduce the qubit resources and circuit depth. Finally, variational quantum eigensolver (VQE) algorithms are employed for ground state estimation where hardware-efficient ansatz circuits are used. To demonstrate the applicability of our methodology, we perform experiments on two tautomeric systems: acetone and Edaravone, each having 52 and 150 spin-orbitals in the Slater Type Orbital - 3 Gaussian (STO-3G) basis set, respectively. Our numerical results show that their tautomeric state prediction agrees with the Coupled Cluster Singles and Doubles (CCSD) benchmarks. Moreover, the required quantum resources are efficient: in the example of Edaravone, we could achieve chemical accuracy with only eight qubits and 80 two-qubit gates.

Origin-Independent Dynamic Polarizability Density from Coupled Cluster Response Theory.

The calculation of the origin-independent density of the dynamic electric dipole polarizability, previously presented for uncorrelated and density functional theory (DFT)-based methods, has been developed and implemented at the coupled cluster singles and doubles (CCSD) level of theory. A pointwise analysis of polarizability densities calculated for a number of molecules at Hartree-Fock (HF) and CCSD clearly shows that the electron correlation effect is much larger than one would argue considering the integrated dipole electric polarizability alone. Large error compensations occur during the integration process, which hide fairly large deviations mainly located in the internuclear regions. The same is observed when calculated CCSD and B3LYP polarizability densities are compared, with the remarkable feature that positive/negative deviations between CCSD and HF reverse sign, becoming negative/positive when comparing CCSD to B3LYP.

Streamlining and Optimizing Strategies of Electrostatic Parameterization.

Accurate characterization of electrostatic interactions is crucial in molecular simulation. Various methods and programs have been developed to obtain electrostatic parameters for additive or polarizable models to replicate electrostatic properties obtained from experimental measurements or theoretical calculations. Electrostatic potentials (ESPs), a set of physically well-defined observables from quantum mechanical (QM) calculations, are well suited for optimization efforts due to the ease of collecting a large amount of conformation-dependent data. However, a reliable set of QM ESP computed at an appropriate level of theory and atomic basis set is necessary. In addition, despite the recent development of the PyRESP program for electrostatic parameterizations of induced dipole-polarizable models, the time-consuming and error-prone input file preparation process has limited the widespread use of these protocols. This work aims to comprehensively evaluate the quality of QM ESPs derived by eight methods, including wave function methods such as Hartree-Fock (HF), second-order Møller-Plesset (MP2), and coupled cluster-singles and doubles (CCSD), as well as five hybrid density functional theory (DFT) methods, used in conjunction with 13 different basis sets. The highest theory levels CCSD/aug-cc-pV5Z (a5z) and MP2/aug-cc-pV5Z (a5z) were selected as benchmark data over two homemade data sets. The results show that the hybrid DFT method, ωB97X-D, combined with the aug-cc-pVTZ (a3z) basis set, performs well in reproducing ESPs while taking both accuracy and efficiency into consideration. Moreover, a flexible and user-friendly program called PyRESP_GEN was developed to streamline input file preparation. The restraining strengths, along with strategies for polarizable Gaussian multipole (pGM) model parameterizations, were also optimized. These findings and the program presented in this work facilitate the development and application of induced dipole-polarizable models, such as pGM models, for molecular simulations of both chemical and biological significance.

Total and orbital density-based analyses of molecules revealing long-range interaction regions.

Total and orbital electron densities of molecules are explored for the effect of the long-range correction (LC) for density functional theory (DFT) exchange functionals by comparing to the effect of the ab initio coupled cluster singles and doubles (CCSD) method. Calculating the LC effect on the total electron densities shows that the LC stabilizes the electrons around the long-range interaction regions of kinetic energy density, which are assumed to be electrons other than free electrons and self-interacting electrons, while the CCSD method stabilizes the electrons in the long-range interaction regions in the vertical molecular planes. As a more precise test, the LC effect on orbital densities are compared to the CCSD effect on Dyson orbital densities. Surprisingly, these effects are similar for the unoccupied orbitals, indicating that the LC covers the effects required to reproduce the CCSD Dyson unoccupied orbitals. For exploring the discrepancies between these effects on the occupied orbitals, the photoionization cross sections are calculated as a direct test for the shapes of the HOMOs to investigate the differences between these effects on the occupied orbitals. Consequently, the LC clearly produces the canonical HOMOs close to the CCSD Dyson and experimental ones, except for the HOMO of benzene molecule that mixes with the HOMO 1 for the CCSD Dyson orbitals. This indicates that the orbital analyses using the photoionization cross sections are available as a direct test for the quality of DFT functionals.

Hyperfine and P, T odd properties in BiO: comparison between coupled-cluster method and multi-reference perturbation method based on a Dirac Hamiltonian

Polar diatomic molecules are attractive in the search for the electron electric dipole moment (eEDM) and the scalar-pseudoscalar (S-PS) interaction, both of which violate time-reversal and parity symmetries. In this study, we examined the electronic ground state of BiO and evaluated the effective electric field (E eff) of eEDM and the W s coefficients of the S-PS interaction. BiO forms a complex chemical bond due to the open-shell configurations of Bi (6p) and O (2p). Consequently, we performed four-component relativistic calculations using complete-active-space second-order perturbation theory (CASPT2), as well as coupled-cluster singles and doubles (CCSD) and CCSD perturbative triples (CCSD(T)) methods. Our analysis revealed that BiO exhibited a multiconfigurational character, as the Hartree-Fock configuration accounted for only 68% of the reference wave function for CASPT2. Nevertheless, for the hyperfine coupling constant (A//), CCSD and CCSD(T) reproduced the experimental value better than CASPT2, indicating that CC methods can capture important excited configurations, rendering multireference treatment unnecessary. The deficiency of CASPT2 in reproducing A// could be attributed to the inadequate treatment of orbital relaxation effects. Our proposed values of E eff and W s for BiO (17 GV/cm and −36 kHz, respectively), derived at the CCSD level, were moderately large for the parity, time-odd experiment.

Periodic Bootstrap Embedding.

Bootstrap embedding (BE) is a recently developed electronic structure method that has shown great success at treating electron correlation in molecules. Here, we extend BE to treat surfaces and solids where the wave function is represented in periodic boundary conditions using reciprocal space sums (i.e., k-point sampling). The major benefit of this approach is that the resulting fragment Hamiltonians carry no explicit dependence on the reciprocal space sums, allowing one to apply traditional nonperiodic electronic structure codes to the fragments even though the entire system requires careful consideration of periodic boundary conditions. Using coupled cluster singles and doubles (CCSD) as an example method to solve the fragment Hamiltonians, we present minimal basis set CCSD-in-HF results on 1D conducting polymers. We show that periodic BE-CCSD can typically recover ∼99.9% of the electron correlation energy. We further demonstrate that periodic BE-CCSD is feasible even for complex donor-acceptor polymers of interest to organic solar cells─despite the fact that the monomers are sufficiently large that even a Γ-point periodic CCSD calculation is prohibitive. We conclude that BE is a promising new tool for applying molecular electronic structure tools to solids and interfaces.

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin-Spin Coupling Constants Involving Selenium.

We present new compact pecJ-n (n = 1, 2) basis sets for the selenium atom developed for the quantum-chemical calculations of NMR spin-spin coupling constants (SSCCs) involving selenium nuclei. These basis sets were obtained at the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes (SOPPA(CCSD)) level with the property-energy consistent (PEC) method, which was introduced in our previous papers. The existing SSCC-oriented selenium basis sets are rather large in size, while the PEC method gives more compact basis sets that are capable of providing accuracy comparable to that reached using the property-oriented basis sets of larger sizes generated with a standard even-tempered technique. This is due to the fact that the PEC method is very different in its essence from the even-tempered approaches. It generates new exponents through the total optimization of angular spaces of trial basis sets with respect to the property under consideration and the total molecular energy. New basis sets were tested on the coupled cluster singles and doubles (CCSD) calculations of SSCCs involving selenium in the representative series of molecules, taking into account relativistic, solvent, and vibrational corrections. The comparison with the experiment showed that the accuracy of the results obtained with the pecJ-2 basis set is almost the same as that provided by a significantly larger basis set, aug-cc-pVTZ-J, while that achieved with a very compact pecJ-1 basis set is only slightly inferior to the accuracy provided by the former.

Toward an efficient implementation of internally contracted coupled-cluster methods.

A new implementation of the internally contracted multireference coupled-cluster with singles and doubles (icMRCCSD) method is presented. The new code employs an efficient tensor contraction kernel and can also avoid full four-external integral transformations, which significantly extends the scope of the applicability of icMRCCSD. The new implementation is currently restricted to the simple case of two active electrons in two orbitals and also supports the computation of spin-adapted doublet and triplet coupled-cluster wavefunctions. This contribution describes the basic approach for the automated derivation of working equations and benchmarks the current code against efficient implementations of standard methods, such as single-reference coupled-cluster singles and doubles (CCSD) and internally contracted multireference configuration interaction (icMRCI). Run times for linearized variants of icMRCCSD are only twice as long as comparable CCSD runs and similar to those of the icMRCI implementation, while non-linear terms of more complete variants of icMRCCSD lead to an order of magnitude longer computation times. Nevertheless, the new code allows for computations at larger scales than it was possible previously, with less demands on memory and disk-space resources. This is exemplified by numerical structure optimizations and harmonic force field determinations of NC2H5 isomers and the singlet and triplet states of m-benzyne. In addition, the exchange coupling of a dinuclear copper complex is determined. This work also defines a new commutator approximation for icMRCCSD, which includes all terms that are also present in the single-reference CCSD method, thus yielding a consistent pair of single-reference and multireference coupled-cluster methods.

Density Matrix Renormalization Group for Transcorrelated Hamiltonians: Ground and Excited States in Molecules.

We present the theory of a density matrix renormalization group (DMRG) algorithm which can solve for both the ground and excited states of non-Hermitian transcorrelated Hamiltonians and show applications in molecular systems. Transcorrelation (TC) accelerates the basis set convergence rate by including known physics (such as, but not limited to, the electron-electron cusp) in the Jastrow factor used for the similarity transformation. It also improves the accuracy of approximate methods such as coupled cluster singles and doubles (CCSD) as shown by recent studies. However, the non-Hermiticity of the TC Hamiltonians poses challenges for variational methods like DMRG. Imaginary-time evolution on the matrix product state (MPS) in the DMRG framework has been proposed to circumvent this problem, but this is currently limited to treating the ground state and has lower efficiency than the time-independent DMRG (TI-DMRG) due to the need to eliminate Trotter errors. In this work, we show that with minimal changes to the existing TI-DMRG algorithm, namely, replacing the original Davidson solver with the general Davidson solver to solve the non-Hermitian effective Hamiltonians at each site for a few low-lying right eigenstates, and following the rest of the original DMRG recipe, one can find the ground and excited states with improved efficiency compared to the original DMRG when extrapolating to the infinite bond dimension limit in the same basis set. An accelerated basis set convergence rate is also observed, as expected, within the TC framework.

New Implementation of an Equation-of-Motion Coupled-Cluster Damped-Response Framework with Illustrative Applications to Resonant Inelastic X-ray Scattering

We present an implementation of a damped response framework for calculating resonant inelastic X-ray scattering (RIXS) at the equation-of-motion coupled-cluster singles and doubles (CCSD) and second-order approximate coupled-cluster singles and doubles (CC2) levels of theory in the open-source program eT. This framework lays the foundation for future extension to higher excitation methods (notably, the coupled-cluster singles and doubles with perturbative triples, CC3) and to multilevel approaches. Our implementation adopts a fully relaxed ground state and different variants of the core-valence separation projection technique to address convergence issues. Illustrative results are compared with those obtained within the frozen-core core-valence separated approach, available in Q-Chem, as well as with experiment. The performance of the CC2 method is evaluated in comparison with that of CCSD. It is found that, while the CC2 method is noticeably inferior to CCSD for X-ray absorption spectra, the quality of the CC2 RIXS spectra is often comparable to that of the CCSD level of theory, when the same valence excited states are probed. Finally, we present preliminary RIXS results for a solvated molecule in aqueous solution.

Cluster-in-Molecule Method Combined with the Domain-Based Local Pair Natural Orbital Approach for Electron Correlation Calculations of Periodic Systems.

The cluster-in-molecule (CIM) method was extended to systems with periodic boundary conditions (PBCs) in a previous work (PBC-CIM) [J. Chem. Theory Comput.2019, 15, 2933], which is able to compute the electronic structures of periodic systems at second-order Møller-Plesset perturbation theory (MP2) and coupled cluster singles and doubles (CCSD) levels. However, the high computational costs of CCSD with respect to the size of clusters limit the usage of PBC-CIM to crystals with small or medium unit cells. In this work, we further develop the PBC-CIM method by employing the domain-based local pair natural orbital (DLPNO) methods for the electron correlation calculations of clusters to reduce the computational costs. The combined approach allows CCSD with perturbative triples, denoted as CCSD(T), to be computationally available for accurate descriptions of periodic systems. The distant-pair correction is also implemented to improve the accuracy of PBC-CIM. As in the molecular cases, the distant pair correction significantly improves the accuracy of various PBC-CIM methods with few additional costs. The PBC-CIM-DLPNO-CCSD(T) approach has been applied to investigate the optimized lattice parameter of the cubic LiCl crystal and two adsorption problems (CO on the NaCl(100) surface and H2O on the h-BN surface). The results show that the CIM-DLPNO-CCSD(T) method offers accurate and efficient descriptions for the studied systems. Another application to the cohesive energy of the acetic acid crystal reveals that large basis sets are necessary for reliable calculations on the cohesive energies of molecular crystals.

Periodic Coupled-Cluster Green's Function for Photoemission Spectra of Realistic Solids.

We present an efficient implementation of the coupled-cluster Green's function (CCGF) method for simulating photoemission spectra of periodic systems. We formulate the periodic CCGF approach with Brillouin zone sampling in the Gaussian basis at the coupled-cluster singles and doubles (CCSD) level. To enable CCGF calculations of realistic solids, we propose an active-space self-energy correction scheme by combining CCGF with the cheaper many-body perturbation theory (GW) and implement the model order reduction (MOR) frequency interpolation technique. We find that the active-space self-energy correction and MOR techniques significantly reduce the computational cost of CCGF while maintaining the high accuracy. We apply the developed CCGF approaches to compute spectral properties and band structure of silicon (Si) and zinc oxide (ZnO) crystals using triple-ζ Gaussian basis sets and medium-size k-point sampling and find good agreement with experimental measurements.

A Quantum Chemical Investigation into the Molecular Mechanism of the Atmospheric Reactions of Chemi-Ions with Nitrogen and Nitrogen Oxides.

Nitrogen oxides and chemi-ions are atmospheric pollutants with considerable aeronomic interest. These toxicants can react with each other, producing various ionic species and highly reactive by-products that play a crucial role in aerosol clustering and mediate several important atmospheric reactions. Understanding the chemical reactivity of these pollutants can provide essential information for controlling their excess emission into the atmosphere. Computational modeling and electronic structure studies help in predicting the structure, reactivity, and thermodynamics of transient atmospheric chemical species and can guide experimental research by providing vital mechanistic insights and data. In the present study, a computational investigation into the mechanisms of the binary associative reactions between negative ions: O2− and O3− with NO, NO2, and N2 was conducted using the Coupled-Cluster Singles and Doubles (CCSD) theory. Five model reactions between N2/NOx with On− (n = 2, 3) were considered in this work. Our calculations revealed that reactions (2) and (5) are two sequential processes involving intermediates, and all others occur in a concerted manner by direct transitions from the reactants to the products, with no isolable intermediates proceeding via single non-planar transition states. Our study revealed that the higher activation barrier required for the formation of NO3− (2) as compared to NO2− (1) could be the reason for the excess formation of NO2− ions over NO3− ions in the atmosphere. Further, all the investigated reactions except (5) are found to be feasible at room temperature. The energy required to break N-N bonds in the N2 molecule justifies the high barrier for (5). The results obtained from the study are in close agreement with the available experimental data. Moreover, the data from the study can be utilized for the evaluation of experiments and model predictions pertaining to NOx oxidation and molecular modeling of the gas-phase chemistry of pollutants/nucleation precursors formed in the Earth’s atmosphere and aircraft engines.

Oscillator Strengths in the Framework of Equation of Motion Multilevel CC3.

We present an efficient implementation of the equation of motion oscillator strengths for the closed-shell multilevel coupled cluster singles and doubles with perturbative triples method (MLCC3) in the electronic structure program eT. The orbital space is split into an active part treated with CC3 and an inactive part computed at the coupled cluster singles and doubles (CCSD) level of theory. Asymptotically, the CC3 contribution scales as floating-point operations, where nV is the total number of virtual orbitals while nv and no are the number of active virtual and occupied orbitals, respectively. The CC3 contribution, thus, only scales linearly with the full system size and can become negligible compared to the cost of CCSD. We demonstrate the capabilities of our implementation by calculating the ultraviolet–visible spectrum of azobenzene and a core excited state of betaine 30 with more than 1000 molecular orbitals.