Local Orbitals Method Research Articles

Bandgap tuning and thermoelectric characteristics of Sc-based double halide perovskites K2ScAgZ6 (Z = Cl, Br, I) for solar cells applications

Using the full-potential linearized augmented plane wave plus local orbitals method within the frame work of density functional theory, the Sc-based double halide perovskites K2ScAgZ6 (Z = Cl, Br, I) are investigated for determining their physical properties. To investigate the structural and thermodynamic stability of these Sc-based double halide perovskites we calculate tolerance factor, formation energy, and phonon dispersion curve using GGA-PBEsol approximation. The calculated values of lattice parameters using GGA-PBEsol are found to be consistent with the available data. Subsequently, the Tran-Blaha modified Becke-Johnson (mBJ-LDA) potential is used for electronic properties. Implementation of TB-mBJ potential is clearly shows that K2ScAgZ6 have indirect bandgap, which is consistent with the literature. To evaluate these double perovskites and reveal their potential use in optical devices, several optical parameters are computed for an incident photon energy range of 0–8 eV. The BoltzTraP code is also employed to investigate temperature dependent electrical characteristic of these compounds in the temperature range of 200–600 K. Investigated halide double-perovskites have been shown to display excellent physical properties for solar cells and renewable energy device applications.

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.

First-principles computation of the electronic structure and optical properties of Tl3PbBr5 and TlPb2Br5: Application of the TB-mBJ+U+SOC technique

Results of computation of the electronic structure of low-temperature (LT) orthorhombic (space group P212121) and high-temperature (HT) tetragonal (space group P41) polymorphous forms of Tl3PbBr5 as well as of TlPb2Br5 (monoclinic space group P21/c) compound as compared to the experimental XPS studies of these bromides are presented. Our results indicate that the best correspondence of the theoretical total density of states and the experimental XPS valence-band spectrum is detected when the computations are carried out employing the augmented plane wave + local orbitals method within a Density Functional Theory (DFT) formalism and using the modified Becke-Johnson (mBJ) functional as refined by Tran-Blaha and considering also the Hubbard correction parameter U for strongly correlated d electrons associated with Tl and Pb atoms and spin-orbit coupling (SOC) effect (TB-mBJ + U + SOC technique). Based on these findings, using the mBJ + U + SOC technique, we study in detail partial densities of states of LT- and HT-modifications of Tl3PbBr5 and of TlPb2Br5. Furthermore, for the above ternary bromides, for the first time, the main optical properties were calculated.

First-principles WC-GGA and mBJ calculations for structural, electronic, optical and elastic properties of MxGa1-xSb (M=Al, In, B) ternary alloys

GaSb based ternary alloys have indicated wide range variations in physical, electronic and optical properties. In the present study the structural, electronic, optical and elastic properties of MxGa1-xSb (M = Al, In, B) ternary alloys have been reported and discoursed based on the first-principles investigation. The current work attempts to provide an insight into the evolution of electronic, optical and elastic properties of ternary alloys of MxGa1-xSb (M = Al, In, B) with variation in their constituent compounds. Density functional theory (DFT) operation based on the augmented plane wave + local orbitals (APW + lo) method has been employed to estimate the structure, density of states (DOS), bandstructure, optical and the elastic properties of ternary alloys MxGa1-xSb (M = Al, In, B) for (x = 0, 0.25, 0.50, 0.75, 1) compositions. Computations were performed using the exchange-correlation energy functional from Wu-Cohen, a generalized-gradient approximation (WC-GGA) as well as the original modified Becke-Johnson exchange potential (mBJ) available with the WIEN2k code. As WC-GGA has been observed to underestimate the bandgap, the bandstructure of ternary alloys MxGa1-xSb (M = Al, In, B) for (x = 0, 0.25, 0.50, 0.75, 1) compositions has been reported using modified Becke-Johnson exchange potential (mBJ) method. In case of AlxGa1-xSb and BxGa1-xSb alloys, the bandgap values have been observed to deviate strongly from the Vegards law indicating the existence of a bowing parameter while the bandgap values of InxGa1-xSb alloys are in excellent agreement with the reported values and deviate marginally from the Vegards law. Further the optical properties, real and imaginary parts of ϵ(ω) and loss function of MxGa1-xSb (M = Al, In, B) for ternary alloys have been calculated using WC-GGA. The critical points, peaks and shoulders of imaginary part of dielectric function in these alloys have been reported. The elastic properties of these alloys, Bulk modulus (B), Shear modulus (G), Young modulus (E) and Poisson's coefficient (ν) have also been calculated using the Cubic-elastic and Tetra-elastic packages.

Orbital pair selection for relative energies in the domain-based local pair natural orbital coupled-cluster method

For the accurate computation of relative energies, domain-based local pair natural orbital coupled-cluster [DLPNO-CCSD(T0)] has become increasingly popular. Even though DLPNO-CCSD(T0) shows a formally linear scaling of the computational effort with the system size, accurate predictions of relative energies remain costly. Therefore, multi-level approaches are attractive that focus the available computational resources on a minor part of the molecular system, e.g., a reaction center, where changes in the correlation energy are expected to be the largest. We present a pair-selected multi-level DLPNO-CCSD(T0) ansatz that automatically partitions the orbital pairs according to their contribution to the overall correlation energy change in a chemical reaction. To this end, the localized orbitals are mapped between structures in the reaction; all pair energies are approximated through computationally efficient semi-canonical second-order Møller-Plesser perturbation theory, and the orbital pairs for which the pair energies change significantly are identified. This multi-level approach is significantly more robust than our previously suggested, orbital selection-based multi-level DLPNO-CCSD(T0) ansatz [M. Bensberg and J. Neugebauer, J. Chem. Phys. 155, 224102 (2021)] for reactions showing only small changes in the occupied orbitals. At the same time, it is even more efficient without added input complexity or accuracy loss compared to the full DLPNO-CCSD(T0) calculation. We demonstrate the accuracy of the multi-level approach for a total of 128 chemical reactions and potential energy curves of weakly interacting complexes from the S66x8 benchmark set.

Spin and orbital magnetism of exohedral fullerene doped with single transition metal atom (Sc-Ni): A relativistic density functional theory study

Relativistic density functional theory calculations have been implemented to study the structural configurations, electronic and magnetic properties of exohedral 3d transition metal atoms doping on C60 fullerene (TM-C60) by a full potential local orbital method. The calculated binding energies revealed that the TM-C60 molecules are energetically stable in all adsorption sites. We also found that the TM-doped exohedral C60 complexes are more reactive than pure C60 fullerene. The spin and orbital magnetic moments were also determined. We have indicated that in all of the five adsorption sites, exohedral TM-C60 molecules (except for Ni-C60) are magnetized. Our magnetic calculations show that the total spin magnetic moments of TM-C60 molecules mainly come from the TM atoms. We found that the spin magnetic moments of adsorbed TM atoms in exohedral doping C60 fullerene from Sc to Mn (HH adsorption site) and for Sc to Cr (HP and P adsorption sites) are greater than their free states. Our calculations suggest that exohedral doping 3d TM-C60 complexes can almost maintain spin magnetic moments. We have indicated that the magnetic properties of exohedral TM-C60 molecules change in the presence of spin–orbit coupling. Significant orbital contributions to magnetic moments are recognized in these configurations while the spin moments are unaffected. We found that Co in exohedral doping of C60 fullerene shows a robust orbital moment in all the five adsorption sites.

First-Principles Study of Half Metallic Ferromagnetic and Optical Properties of Nb Doped Cubic ZnS using TB-mBJ Approximation

Structural, electronic and optical properties of niobium doped ZnS are studied by using full-potential linearized augmented plane wave plus local orbital (FPLAPW+lo) method within the density functional theory (DFT). Computed results of Nb doped ZnS are compared with that of the pristine zinc blende. Tran-Blaha approach of modified Becke and Johnson local spin density approximation (TB-mBJ) is used to study electronic and optical properties. Estimated result shows that Nb reduces the bandgap of ZnS due to hybridization of Nb-4d orbital with S-3p orbital near the Fermi level. Niobium dopant provides half metallic nature to ZnS with 100% spin polarization. Maximum photo-response is noticed in the ultraviolet range for Zn1-xNbxS (x = 25, 12.5, 6.25 %). Highest peaks are shifted toward the lower energy range for higher dopant percentage. All these suggest that Nb doped ZnS solid solutions are suitable candidate for both energy filter of UV spectrum and spintronic device. Dhaka Univ. J. Sci. 69(3): 194-201, 2022 (June)

Describing Chemical Reactivity with Frontier Molecular Orbitalets.

Locality in physical space is critical in understanding chemical reactivity in the analysis of various phenomena and processes in chemistry, biology, and materials science, as exemplified in the concepts of reactive functional groups and active sites. Frontier molecular orbitals (FMOs) pinpoint the locality of chemical bonds that are chemically reactive because of the associated orbital energies and thus have achieved great success in describing chemical reactivity, mainly for small systems. For large systems, however, the delocalization nature of canonical molecular orbitals makes it difficult for FMOs to highlight the locality of the chemical reactivity. To obtain localized molecular orbitals that also reflect the frontier nature of the chemical processes, we develop the concept of frontier molecular orbitalets (FMOLs) for describing the reactivity of large systems. The concept of orbitalets was developed recently in the localized orbital scaling correction method, which aims for eliminating the delocalization error in common density functional approximations. Orbitalets are localized in both physical and energy spaces and thus contain both orbital locality and energy information. The FMOLs are thus the orbitalets with energies highest among occupied orbitalets and lowest among unoccupied ones. The applications of FMOLs to hexadeca-1,3,5,7,9,11,13,15-octaene in its equilibrium geometry, inter- and intra-molecular charge-transfer systems, and two transition states of a bifurcating reaction demonstrate that FMOLs can connect quantum mechanical treatments of chemical systems and chemical reactivities by locating the reactive region of large chemical systems. Therefore, FMOLs extend the role of FMOs for small systems and describe the chemical reactivity of large systems with energy and locality insight, with potentially broad applications.

Zirconium aluminides studied with first principles calculations: Hyperfine interactions and site preference of dopants

By means of a density functional theory (DFT) based augmented plane waves plus local orbitals (APW ​+ ​lo) method, we study the electric field gradients (EFG) in Ta and Cd-doped Zr–Al intermetallics. Comparing the obtained results with the experimental data obtained from the perturbed angular correlation (PAC) measurements, we conclude that Ta atoms always replace Zr in all the investigated compounds. Our results confirmed the previous experimental assumption that Cd substitutes exclusively for Al in ZrAl3 and Zr2Al3. In the case of Zr2Al our calculations suggest that Cd can probably substitute on both Zr and Al lattice sites, while in Zr3Al, it is most likely to occupy Al position. The effects of the distance between the impurity atoms in the supercells and the deviation of the c/a ratio are also discussed.

Electronic structure and magnetic properties investigation of cubic Fe3O4

We present the results of ab initio calculations of cubic magnetite Fe3O4, investigated by using the full-potential linearized augmented plane wave (FP-LAPW) + local orbitals (lo) method within the limit of density functional theory (DFT). The computed density of states (DOS) shows the distribution of cations in the octahedral sites give rise to half-metallic behavior. The magnetocrystalline anisotropy energy (MAE) computed in this work with generalized gradient approximation (GGA) by both the total energy calculations and magnetic force theorem are equal to −2.923 × 104 J/m3 and −2.021 × 104 J/m3 respectively comparable to the experimentally observed value of −2.0 × 104 J/m3.

Chromone-methanol clusters in the electronic ground and lowest triplet state: a delicate interplay of non-covalent interactions.

Chromone offers two energetically almost equivalent docking sites for alcohol molecules, in which the hydroxyl group is hydrogen bonded to one of the free electron pairs of the carbonyl O atom. Here, the delicate balance between these two competing arrangements is studied by combining IR/R2PI and UV/IR/UV spectroscopy in a molecular beam supported by quantum-chemical calculations. Most interestingly, chromone undergoes an efficient intersystem crossing into the triplet manifold upon electronic excitation, so that the studies on aromatic molecule-solvent complexes are for the first time extended to such a cluster in a triplet state. As the lowest triplet state (T1) is of ground state character, powerful energy decomposition approaches such as symmetry-adapted perturbation theory (SAPT) and local energy decomposition using the domain-based local pair natural orbital coupled-cluster method (DLPNO-CCSD(T)/LED) are applied. From the theoretical analysis we infer for the T1 state a loss of planarity (puckering) of the 4-pyrone ring of the chromone unit, which considerably affects the interplay between different types of non-covalent interactions at the two possible binding sites.

First principle investigation of Niobium (Nb) doped MgO

This paper presents the structural, electronic, and magnetic properties of pure and Nb doped MgO, in its zinc blende and rock salt phase for small concentration. In our work, the full potential linearized augmented plane wave plus local orbital (FP-LAPW + lo) method, implemented in the WIEN2K simulation package and the Local Density Approximation (LDA) were employed. The results obtained show that pure MgO has a gap of 4.97 eV and Mg0.875Nb0.125O has a metallic character. The modifications in the band gap and magnetic properties of magnesium oxide mainly originate from the 4 d-orbitals of the Nb atoms. In comparison with Mg and O atoms (0.007 and 0.054), the magnetic data shows that the Niobium magnetic moment (1.3528 µβ) is the dominant one. As a result, the total magnetic moment of our component is equals to 2.9091 µβ. We consider that MgO and Mg0.875Nb0.125O could be promising candidates for electronic systems and related fields.

Direct orbital selection within the domain-based local pair natural orbital coupled-cluster method.

Domain-based local pair natural orbital coupled cluster (DLPNO-CC) has become increasingly popular to calculate relative energies (e.g., reaction energies and reaction barriers). It can be applied within a multi-level DLPNO-CC-in-DLPNO-CC ansatz to reduce the computational cost and focus the available computational resources on a specific subset of the occupied orbitals. We demonstrate how this multi-level DLPNO-CC ansatz can be combined with our direct orbital selection (DOS) approach [M. Bensberg and J. Neugebauer, J. Chem. Phys. 150, 214106 (2019)] to automatically select orbital sets for any multi-level calculation. We find that the parameters for the DOS procedure can be chosen conservatively such that they are transferable between reactions. The resulting automatic multi-level DLPNO-CC method requires no user input and is extremely robust and accurate. The computational cost is easily reduced by a factor of 3 without sacrificing accuracy. We demonstrate the accuracy of the method for a total of 61 reactions containing up to 174 atoms and use it to predict the relative stability of conformers of a Ru-based catalyst.

First-principles calculations of the high-pressure behavior, electronic, magnetic, and elastic properties of praseodymium pnictides: PrX (X = P, As and Bi)

We report ab-initio calculation of the structural, magnetic, elastic, and electronic properties of the PrX (X = P, As and Bi). The structural stability and phase transition of PrX (X = P, As, Bi) compounds in (NaCl-type), (CsCl-type), (Zinc blende-type), WC-Bh (Hexagonal) and L10 (Tetragonal) structures in ferromagnetic state are investigated using the augmented plane wave plus local orbital (APW + lo) method within GGA + U, and mBJ-GGA + U approximations. Careful inspection of electronic properties indicates that most of the compounds exhibit half-metallic behavior. The total magnetic moment of all investigated compounds is obtained to be 2 µB. The mechanical stability test performed on the computed elastic constants Cij demonstrate that investigated compounds are mechanically stable. To elucidate chemical stability, chemical bonds are investigated and found to be mainly characterized by an ionic-covalent mixture. Moreover, elastic anisotropy of all compounds is calculated. Subsequently.

Structural, Electronic and Magnetic Properties of CaSe Doped with 3d (V, Cr and Mn)

We report first-principles investigation on structural, electronic and magnetic properties of 3d transition metal element-doped rock-salt calcium selenide Ca[Formula: see text]TMxSe (TM = V, Cr and Mn) at concentrations [Formula: see text] = 0.0625, 0.125 and 0.25. We performed the calculations in the framework of the density functional theory (DFT) using the full-potential linearized augmented plane waves plus local orbitals (FP-LAPW+lo) method within the Wu–Cohen generalized gradient approximation (WC-GGA) for the structural optimization and the Tran–Blaha modified Becke–Johnson (TBmBJ) potential for the electronic and the magnetic properties. The computed spin-polarized band structures and densities of states show that Ca[Formula: see text]CrxSe compounds at all studied concentrations are half-metallic ferromagnets with a complete spin polarization of 100% at Fermi-level while the Ca[Formula: see text]VxSe and Ca[Formula: see text]MnxSe are ferromagnetic semiconductors. The total magnetic moments for Ca[Formula: see text]VxSe, Ca[Formula: see text]CrxSe, and Ca[Formula: see text]MnxSe show the integer values of 3[Formula: see text][Formula: see text], 4[Formula: see text][Formula: see text], and 5[Formula: see text][Formula: see text], respectively, with a major contribution of transition metal elements (TM) in the total magnetization. Also, we reported the calculated exchange constants [Formula: see text] and [Formula: see text] and the band edge spin splitting of the valence ([Formula: see text]) and conduction ([Formula: see text]) bands. The ferromagnetism of these compounds is due to the super-exchange and the double-exchange mechanisms in addition to the strong p–d exchange interaction. Therefore, the predicted results indicate that the diluted Ca[Formula: see text]TMxSe (TM = V, Cr, Mn) compounds are suitable candidates for a possible application in the field of spintronic technology.

A DLPNO-CCSD(T) benchmarking study of intermolecular interactions of ionic liquids.

The accuracy of correlation energy recovered by coupled cluster single-, double-, and perturbative triple-excitations, CCSD(T), has led to the method being considered the gold standard of computational chemistry. The application of CCSD(T) has been limited to medium-sized molecular systems due to its steep scaling with molecular size. The recent development of alternative domain-based local pair natural orbital coupled-cluster method, DLPNO-CCSD(T), has significantly broadened the range of chemical systems to which CCSD(T) level calculations can be applied. Condensed systems such as ionic liquids (ILs) have a large contribution from London dispersion forces of up to 150 kJ mol-1 in large-scale clusters. Ionic liquids show appreciable charge transfer effects that result in the increased valence orbital delocalization over the entire ionic network, raising the question whether the application of methods based on localized orbitals is reliable for these semi-Coulombic materials. Here the performance of DLPNO-CCSD(T) is validated for the prediction of correlation interaction energies of two data sets incorporating single-ion pairs of protic and aprotic ILs. DLPNO-CCSD(T) produced results within chemical accuracy with tight parameter settings and a non-iterative treatment of triple excitations. To achieve spectroscopic accuracy of 1 kJ mol-1 , especially for hydrogen-bonded ILs and those containing halides, the DLPNO settings had to be increased by two orders of magnitude and include the iterative treatment of triple excitations, resulting in a 2.5-fold increase in computational cost. Two new sets of parameters are put forward to produce the performance of DLPNO-CCSD(T) within chemical and spectroscopic accuracy.

Spin-polarized electronic and magnetic properties of Ruddlesden-Popper Nd2MO4 (M = Sc and Y) compounds

The first principle calculations on the structural, electronic structure as well as the magnetic properties of Ruddlesden-Popper Nd2MO4 (M = Sc and Y) compounds were accomplished by using the full-potential linearized augmented plane waves with local orbitals (FP-LAPW + lo) method within the spin-polarized density functional theory (spin-DFT) and implemented in the WIEN2k package. The exchange and correlation potential was treated with the generalized gradient approximation PBE-GGA for the structural properties. Moreover, the PBE-GGA + U approximation (where U is the Hubbard correlation term) is used to treat “d” and “f” electrons for the electronic and magnetic properties of these compounds. The equilibrium structural parameters such as: lattice constants (a0 and c0), bulk modulus (B0) and the first pressure-derivative of bulk modulus (B’), are optimized for all these alloys. The calculations of the electronic properties for the Ruddlesden-Popper Nd2MO4 (M = Sc and Y) compounds at their equilibrium lattice parameters disclose that the both compounds are half-metallic materials. The magnetic properties show that the total magnetic moment for the two Nd2ScO4 and Nd2YO4 compounds is found in integer value. The magnetic moment of Nd is reduced from its free space charge value of 4μB, whereas small magnetic moments are produced on the nonmagnetic O1 and O2 sites.

The Role of Spike Protein Mutations in the Infectious Power of SARS-COV-2 Variants: A Molecular Interaction Perspective.

Specific S477N, N501Y, K417N, K417T, E484K mutations in the receptor binding domain (RBD) of the spike protein in the wild type SARS‐COV‐2 virus have resulted, among others, in the following variants: B.1.160 (20A or EU2, first reported in continental Europe), B1.1.7 (α or 20I501Y.V1, first reported in the United Kingdom), B.1.351 (β or 20H/501Y.V2, first reported in South Africa), B.1.1.28.1 (γ or P.1 or 20J/501Y.V3, first reported in Brazil), and B.1.1.28.2 (ζ, or P.2 or 20B/S484K, also first reported in Brazil). From the analysis of a set of bonding descriptors firmly rooted in the formalism of quantum mechanics, including Natural Bond Orbitals (NBO), Quantum Theory of Atoms In Molecules (QTAIM) and highly correlated energies within the Domain Based Local Pair Natural Orbital Coupled Cluster Method (DLPNO‐CCSD(T)), and from a set of computed electronic spectral patterns with environmental effects, we show that the new variants improve their ability to recognize available sites to either hydrogen bond or to form salt bridges with residues in the ACE2 receptor of the host cells. This results in significantly improved initial virus⋅⋅⋅cell molecular recognition and attachment at the microscopic level, which trigger the infectious cycle.

Coupled Cluster Benchmark of New DFT and Local Correlation Methods: Mechanisms of Hydroarylation and Oxidative Coupling Catalyzed by Ru(II, III) Chloride Carbonyls.

We have evaluated a set of accurate canonical CCSD(T) energies for stationary points on the potential energy surface for Ru(II, III) chloride carbonyl catalysis of two competing reactions between benzene and methyl acrylate (MA), namely, hydroarylation and oxidative coupling. We have then applied this set to evaluate the performance of localized orbital coupled-cluster methods and several new and common density functionals. We find that (a) DLPNO-CCSD(T) with TightPNO cutoffs is an acceptable substitute for full canonical CCSD(T) calculations on this system; (b) for the closed-shell systems where it could be applied, LNO-CCSD(T) with tight convergence criteria is very close to the canonical results; (c) the recent ωB97X-V and ωB97M-V functionals exhibit superior performance to commonly used DFT functionals in both closed- and open-shell calculations; (d) the revDSD-PBEP86 revision of the DSD-PBEP86 double hybrid represents an improvement over the original, even though transition metals were not involved in its parametrization; and (e) DSD-SCAN and DOD-SCAN show comparable efficiency. Most tested (meta)-GGA and hybrid density functionals perform better for open-shell than for closed-shell complexes; this is not the case for the double hybrids considered.

Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory.

A nearly linear scaling implementation of coupled-cluster with singles and doubles excitations (CCSD) can be achieved by means of the domain-based local pair natural orbital (DLPNO) method. The combination of DLPNO-CCSD with implicit solvation methods allows the calculation of accurate energies and chemical properties of solvated systems at an affordable computational cost. We have efficiently implemented different schemes within the conductor-like polarizable continuum model (C-PCM) for DLPNO-CCSD in the ORCA quantum chemistry suite. In our implementation, the overhead due to the additional solvent terms amounts to less than 5% of the time the equivalent gas phase job takes. Our results for organic neutrals and open-shell ions in water show that for most systems, adding solvation terms to the coupled-cluster amplitudes equations and to the energy leads to small changes in the total energy compared to only considering solvated orbitals and corrections to the reference energy. However, when the solute contains certain functional groups, such as carbonyl or nitrile groups, the changes in the energy are larger and estimated to be around 0.04 and 0.02 kcal/mol for each carbonyl and nitrile group in the solute, respectively. For solutes containing metals, the use of accurate CC/C-PCM schemes is crucial to account for correlation solvation effects. Simultaneously, we have calculated the electrostatic component of the solvation energy for neutrals and ions in water for the different DLPNO-CCSD/C-PCM schemes. We observe negligible changes in the deviation between DLPNO-CCSD and canonical-CCSD data. Here, DLPNO-CCSD results outperform those for Hartree-Fock and density functional theory calculations.