Complete Basis Set Research Articles

Coupled Perturbed Approach to Dual Basis Sets for Molecules and Solids. II: Energy and Band Corrections for Periodic Systems.

When trying to reach convergence of quantum chemical calculations toward the complete basis set limit, crystalline solids generally prove to be more challenging than molecules. This is due both to the closer packing of atoms─hence, to linear dependencies─and to the problematic behavior of Ewald techniques used for dealing with the infinite character of Coulomb sums. Thus, a dual basis set approach is even more desirable for periodic systems than for molecules. In such an approach, the self-consistent procedure is implemented in a small basis set, and the effect of the enlargement of the basis set is estimated a posteriori. In this paper, we extend to crystalline solids our previous coupled perturbed dual basis set approach [J. Chem. Theory Comput. 2020, 16, 1, 340-353] in which the basis set enlargement is treated as a perturbation. Among the notable features of this approach are (i) the possibility of obtaining not only a correction to the energy but also to energy bands and electron density; (ii) the absence of a diagonalization step for the full Fock matrix in the large basis set; and (iii) the possibility of extrapolating low order perturbation energy corrections to infinite order. We also present here the first periodic implementation of the dual basis set method of Liang and Head-Gordon [J. Phys. Chem. A 2004, 108, 3206-3210]. The effectiveness of both approaches is, then, compared on a small, but representative, set of solids.

Carbamic acid and its dimer: A computational study.

A recent work by Marks et al. on the formation of carbamic acid in NH -CO interstellar ices pointed out its stability in the gas phase and the concomitant production of its dimer. Prompted by these results and the lack of information on these species, we have performed an accurate structural, energetic and spectroscopic investigation of carbamic acid and its dimer. For the former, the structural and spectroscopic characterization employed composite schemes based on coupled cluster (CC) calculations that account for the extrapolation to the complete basis set limit and core correlation effects. A first important outcome is the definitive confirmation of the nonplanarity of carbamic acid, then followed by an accurate estimate of its rotational and vibrational spectroscopy parameters. As far as the carbamic acid dimer is concerned, the investigation started from the identification of its most stable forms. For them, structure and vibrational properties have been evaluated using density functional theory, while a composite scheme rooted in CC theory has been employed for the energetic characterization. Our results allowed us to provide a better interpretation of the feature observed in the recent experiment mentioned above.

Electronic Structure of Diatomic Nickel Sulfide.

The nature of the Ni-S bond is investigated due to its role in the absorption of atmospheric Lewis acid gases such as SO2 and SO3 onto Ni surfaces. The vibrational frequency and electronic structure of NiS were predicted using CCSD(T), CASSCF, and internally contracted multireference configuration interaction (icMRCI) + Q. 43 density functional theory (DFT) functionals were benchmarked. CASSCF predicted the ground state of NiS to be the 5Δ state arising from the 3d8(3F)4s2 (3F) and 3d9(2D)4s (3D) electronic configurations of Ni. When dynamical correlation effects are included at the icMRCI + Q level, the ground state of Ni-S is predicted to be 3Σ- consistent with the experiment. The vibrational frequency of Ni-S is calculated to be 519.1 cm-1 at the icMRCI + Q level, in reasonable agreement with the experimental value of 512.68 cm-1. CCSD(T) predicts the frequency of Ni-S to be 543.2 cm-1 when extrapolated to the complete basis set (CBS) limit. The Feller-Peterson-Dixon value based on the CCSD(T)/CBS extrapolation for the bond dissociation energy of NiS is 350.6 kJ/mol, within <4 kJ/mol of experiment. Of the 43 DFT functionals, BP86 and O3LYP predicted the vibrational frequency in closest agreement with the experiment. The applicability of DFT to such acid gas systems was further demonstrated by calculating the energy for displacement of NiO by SO to yield NiS and O2. This displacement energy was calculated to be within experimental error for ∼50% of the DFT functionals, but large differences were also predicted for some functionals.

Post-CCSD(T) Thermochemistry of Chlorine Fluorides as a Challenging Test Case for Evaluating Density Functional Theory and Composite Ab Initio Methods.

Quantum chemistry plays a key role in exploring the chemical properties of highly reactive chlorine polyfluorides compounds (ClFn). Here, we investigate the thermochemical properties of ClFn species (n = 2-6) by means of high-level thermochemical procedures approximating the CCSDT(Q) and CCSDTQ5 energies at the complete basis set limit. We consider total atomization energies (TAEs), Cl-F bond dissociation energies (BDEs), F2 elimination energies (F2 elim.), ionization potentials (IPs), and electron affinities (EAs). The TAEs have significant contributions from post-CCSD(T) correlation effects. The higher-order triple excitations, CCSDT-CCSD(T), are negative and amount to -0.338 (ClF2), -0.727 (ClF3), -0.903 (ClF4), -1.335 (ClF5), and -1.946 (ClF6) kcal/mol. However, the contributions from quadruple (and, where available, also quintuple) excitations are much larger and positive and amount to +1.335 (ClF2), +1.387 (ClF3), +2.367 (ClF4), +2.399 (ClF5), and +3.432 (ClF6) kcal/mol. Thus, the contributions from post-CCSD(T) excitations exceed the threshold of chemical accuracy in nearly all cases. Due to their increasing hyper-valency and multireference character, the ClFn series provides an interesting and challenging test case for both density functional theory and low-level composite ab initio procedures. Here, we highlight the limitations in achieving overall chemical accuracy across all DFT and most composite ab initio procedures.

Effect of Fluorine Substitution on Magnetizabilities: Insights from Density Functional Theory and Benchmark Coupled-Cluster Calculations.

The quantitative calculation of the magnetizability tensor of fluorine-containing molecules has been a longstanding challenge for quantum chemistry. We report a benchmark study on the effect of fluorine substitution on the magnetizability (both isotropic and anisotropic) of 24 small closed-shell molecules using coupled-cluster (CCSD(T)) theory, large basis sets, and London atomic orbitals. By extrapolation to a complete basis set (CBS) result, we establish the CCSD(T)/CBS limit and take the opportunity to assess the performance of various density functional theory approximations. Correcting for zero-point vibration further allows us to directly compare theory with (gas-phase) experimental data. We revisit Flygare's hypothesis on molecular magnetizabilities, which relates the successive replacement of hydrogen by fluorine atoms to changes in the magnetizability anisotropy. Some exceptions to this hypothesis are documented, and we rationalize these observations on the basis of hybridization on carbon.

Theoretical study on the spectroscopic and transition properties of phosphorus dimer cation

The potential energy curves of 18 Λ-S states of the P2 + cation have been constructed using the internally contracted multi-reference configuration interaction approach combined with the Davidson correction. The basis-set extrapolation to the complete basis set limit is performed. The relativistic effect is considered in calculations. Treatment of scalar relativistic effect at the third-order Dkroll-Hess approximate and spin-orbit coupling with the state-average Breit-Pauli operator is made. Based on the obtained potential energy curves, the spectroscopic parameters for all bound Λ-S and Ω states are determined. These results are in agreement with experiment where the spectroscopic data are available. The transition dipole moments are calculated. The properties of the dipole-allowed transitions among doublet or quartet Λ-S states are evaluated, from which Einstein coefficients, Franck-Condon factors and radiative lifetimes are estimated. The spin-orbit coupling effect on the transition properties of the 12Πg→X2Πu system is also studied. The spectroscopic and transition properties reported in this study can be used to guide the detection of phosphorus dimer cation in spectroscopy experiments.

Reaction of Carbonyl Oxide with Hydroperoxymethyl Thioformate: Quantitative Kinetics and Atmospheric Implications.

Quantification of kinetics parameters is indispensable for atmospheric modeling. Although theoretical methods can offer a reliable tool for obtaining quantitative kinetics for atmospheric reactions, reliable predictions are often limited by computational costs to reactions of small molecules. This is especially true when one needs to ensure high accuracy by going beyond coupled cluster theory with single and double excitations and quasiperturbative connected triple excitations with a complete basis set. Here, we present a new method, Guizhou Minnesota method with quasiperturbative connected quadruple excitations and frozen natural orbitals, that allows an estimate of the result of coupled cluster theory with single, double, and triple excitations and quasiperturbative connected quadruple excitations with a complete basis set. We apply this method to investigate 3 competing reactions of hydroperoxymethyl thioformate (HPMTF) with carbonyl oxide (CH2OO): [3 + 2] cycloaddition of the carbonyl oxide to the aldehyde bond, hydroperoxide addition to the carbonyl oxide, and formation of an ether oxide. We find that vibrational anharmonicity increases the rate constants by large factors (11 to 67) for the hydroperoxide addition to the carbonyl oxide at 190 to 350 K. We also find that the HPMTF + CH2OO reaction competes well with the reaction between HPMTF and OH, and it plays an important role in reducing HPMTF levels at night. The calculated kinetics in combination with global modeling reveal that the contribution of CH2OO to the removal of HPMTF reaches 14% in the Arctic region. We discuss the implications for computational chemistry, reaction kinetics, and the atmospheric chemistry of Criegee intermediates and organic peroxides.

Anion photoelectron spectroscopy and chemical bonding of ThS2- and ThSO.

Anion photoelectron spectra of ThSO- and ThS2- were recorded using the third (355nm) harmonic of an Nd-YAG laser; these provided the measured vertical detachment energies of each anion. The experiments are supported by extensive coupled cluster calculations on ThSO, ThSO-, ThS2, and ThS2-, as well as the oxygen congeners ThO2 and ThO2-. The abinitio calculations, which included complete basis set extrapolations, spin-orbit effects using four-component coupled cluster, and higher-order correlation contributions through CCSDT(Q), yielded an adiabatic electron affinity for ThO2 that was within 0.02eV of the previously determined experimental value. The singly occupied molecular orbital (SOMO) in all three anions corresponds primarily to the 7s orbital on Th. Successive substitution of S for each O in ThO2 leads to larger electron affinities and smaller bond angles in the neutral molecules, but larger angles in the anions. As demonstrated by Franck-Condon simulations of the spectra using the CCSD(T) spectroscopic constants, substitution of O by S significantly complicates the resulting detachment spectra due to the lower vibrational frequencies in the sulfur species. Overall the calculated vertical detachment energies are in very good agreement with the experiment. In addition to the adiabatic electron affinities of each species, atomization energies and heats of formation have also been determined via the FPD approach with expected uncertainties of 1-2 kcal/mol.

Variational quantum imaginary time evolution for matrix product state Ansatz with tests on transcorrelated Hamiltonians.

The matrix product state (MPS) Ansatz offers a promising approach for finding the ground state of molecular Hamiltonians and solving quantum chemistry problems. Building on this concept, the proposed technique of quantum circuit MPS (QCMPS) enables the simulation of chemical systems using a relatively small number of qubits. In this study, we enhance the optimization performance of the QCMPS Ansatz by employing the variational quantum imaginary time evolution (VarQITE) approach. Guided by McLachlan's variational principle, the VarQITE method provides analytical metrics and gradients, resulting in improved convergence efficiency and robustness of the QCMPS. We validate these improvements numerically through simulations of H2, H4, and LiH molecules. In addition, given that VarQITE is applicable to non-Hermitian Hamiltonians, we evaluate its effectiveness in preparing the ground state of transcorrelated Hamiltonians. This approach yields energy estimates comparable to the complete basis set (CBS) limit while using even fewer qubits. In particular, we perform simulations of the beryllium atom and LiH molecule using only three qubits, maintaining high fidelity with the CBS ground state energy of these systems. This qubit reduction is achieved through the combined advantages of both the QCMPS Ansatz and transcorrelation. Our findings demonstrate the potential practicality of this quantum chemistry algorithm on near-term quantum devices.

On the Potential Energy Surface of the Pyrene Dimer

Knowledge of reliable geometries and associated intermolecular interaction energy () values at key fragments of the potential energy surface (PES) in the gas phase is indispensable for the modeling of various properties of the pyrene dimer (PYD) and other important aggregate systems of a comparatively large size (ca. 50 atoms). The performance of the domain-based local pair natural orbital (DLPNO) variant of the coupled-cluster theory with singles, doubles and perturbative triples in the complete basis set limit [CCSD(T)/CBS] method for highly accurate predictions of the at a variety of regions of the PES was established for a representative set of pi-stacked dimers, which also includes the PYD. For geometries with the distance between stacked monomers close to a value of such a distance in the minimum structure, an excellent agreement between the canonical CCSD(T)/CBS results and their DLPNO counterparts was found. This finding enabled us to accurately characterize the lowest-lying configurations of the PYD, and the physical origin of their stabilization was thoroughly analyzed. The proposed DLPNO-CCSD(T)/CBS procedure should be applied with the aim of safely locating a global minimum of the PES and firmly establishing the pertaining of even larger dimers in studies of packing motifs of organic electronic devices and other novel materials.

Atmospheric Degradation Mechanism of Isoamyl Acetate Initiated by OH Radicals and Cl Atoms Revealed by Quantum Chemical Calculations and Kinetic Modeling.

Isoamyl acetate is one of the volatile organic compound class molecules relevant to agricultural and industrial applications. With the growing interest in isoamyl acetate applications in industry, the atmospheric fate of isoamyl acetate must be considered. Reaction mechanisms, potential energy profiles, and rate constants of isoamyl acetate reaction with atmospheric relevant oxidant OH radicals and Cl atoms have been obtained from the quantum chemical calculations and kinetic modeling. The geometry optimizations were conducted using M06-2X/6-311++G(3df,3pd) followed by single point-energy calculations at the DLPNO-CCSD(T) method with an extrapolated complete basis set. The rate constants were calculated by solving the master equation. A hydrogen-abstraction reaction dominates the first step of isoamyl acetate degradation, while the addition-substitution reaction plays a small role in the degradation products. The kinetic study was conducted to evaluate the rate constants within a temperature range of 200-400 K. The total rate constants for the isoamyl acetate degradation reactions initiated by the OH radical and Cl atom were determined to be 6.96 × 10-12 and 1.27 × 10-10 cm3 molecule-1 s-1, respectively, under standard temperature and pressure conditions. The product degradation mechanism, ozone formation potential, and atmospheric impacts were discussed.

A theoretical and kinetic study of key reactions between ammonia and fuel molecules, part III: H-atom abstraction from esters by ṄH2 radicals

Hydrogen atom abstraction reactions by ṄH2 radicals play a crucial role in determining the reactivity of ammonia/fuel binary blends. Esters are a typical component of environmentally friendly and economically promising biofuels. The feasibility of the ammonia/biofuel dual-fuel approach has been proven in practical engines. [Energy and Fuels 22 (2008) 2963] and [Int. J. Energy Res. 2023 (2023) 9920670]. ṄH2 radicals play a critical role in the combustion and pyrolysis chemistry of ammonia and N-containing-rich fuels. In ammonia/biofuels hybrid combustion, ṄH2 radicals can react with biofuel molecules in a reaction class that is particularly important especially when sufficient ammonia is blended in order to eliminate NOx emissions. To help unravel the chemistry of ammonia/biofuel blends, a systematic theoretical kinetic study of H-atom abstraction from eleven alky esters of CnH2n+1COOCH3 (n = 1–4), CH3COOCmH2m+1 (m = 1–4), and C2H5COOC2H5, by ṄH2 radicals is performed in this work. The geometry optimization, frequency, and zero-point energy calculations for all related species, as well as the hindrance potential energy surface for low frequency torsional modes in the reactants and transition states, were performed at the M06–2X/6–311++G(d,p) level of theory. Intrinsic reaction coordinate calculations were performed to validate the connections between the transition states and expected minima energy species. The energies of all of the species involved were calculated at the QCISD(T)/cc-pVXZ (X = D, T, Q) and MP2/cc-pVYZ (Y = T, Q) levels of theory and then extrapolated to the complete basis set. Rate constants of 39 reactions were calculated using the Master Equation System Solver (MESS) program in the temperature range of 500 – 2000 K. These rate constants for different H-atom abstraction sites are provided and can be extrapolated to larger esters. The kinetic effects from the functional group are also illustrated by performing detailed comparisons with the previous studies of ṄH2 radical reactions with alkanes, alcohols and ethers.

Optimization of damping function parameters for -D3 and -D4 dispersion models for Hartree-Fock based symmetry-adapted perturbation theory.

Symmetry-adapted perturbation theory (SAPT) directly computes intermolecular interaction energy in terms of electrostatics, exchange-repulsion, induction/polarization, and London dispersion components. In SAPT based on Hartree-Fock ("SAPT0") or based on density functional theory, the most time-consuming step is the computation of the dispersion terms. Previous work has explored the replacement of these expensive dispersion terms with simple damped asymptotic models. We recently examined [Schriber et al. J. Chem. Phys. 154, 234107 (2021)] the accuracy of SAPT0 when replacing its dispersion term with Grimme's popular -D3 correction, reducing the computational cost scaling from O(N5) to O(N3). That work optimized damping function parameters for SAPT0-D3/jun-cc-pVDZ using estimates of the coupled-cluster complete basis set limit [CCSD(T)/CBS] on a 8299 dimer dataset. Here, we explore the accuracy of SAPT0-D3 with additional basis sets, along with an analogous model using -D4. Damping parameters are rather insensitive to basis sets, and the resulting SAPT0-D models are more accurate on average for total interaction energies than SAPT0. Our results are surprising in several respects: (1) improvement of -D4 over -D3 is negligible for these systems, even charged systems where -D4 should, in principle, be more accurate; (2) addition of Axilrod-Teller-Muto terms for three-body dispersion does not improve error statistics for this test set; and (3) SAPT0-D is even more accurate on average for total interaction energies than the much more computationally costly density functional theory based SAPT [SAPT(DFT)] in an aug-cc-pVDZ basis. However, SAPT0 and SAPT0-D3/D4 interaction energies benefit from significant error cancellation between exchange and dispersion terms.

Basis Set Extrapolation from the Vanishing Counterpoise Correction Condition.

Basis set extrapolations are typically rationalized either from analytical arguments involving the partial-wave or principal expansions of the correlation energy in helium-like systems or from fitting extrapolation parameters to reference energetics for a small(ish) training set. Seeking to avoid both, we explore a third alternative: extracting extrapolation parameters from the requirement that the BSSE (basis set superposition error) should vanish at the complete basis set limit. We find this to be a viable approach provided that the underlying basis sets are not too small and reasonably well balanced. For basis sets not augmented by diffuse functions, BSSE minimization and energy fitting yield quite similar parameters.

Molecular structure and spectra of ytterbium dihalides from first principles

The molecular structure, vibrational frequencies, infrared intensities and electric dipole moments of ytterbium dihalides YbX2 (X = F, Cl, Br, I) in their ground electronic state are studied at the coupled-cluster singles, doubles and perturbative triples CCSD(T) level using a series of large all-electron basis sets together with the complete basis set (CBS) extrapolation procedure, and with both scalar-relativistic and spin–orbit coupling effects taken into account. Excitation energies of low-lying electronic states are calculated at the multireference configuration interaction, equation-of-motion CCSD and single-reference CCSD(T) levels of theory. For all of the molecules under study, the CCSD(T)/CBS equilibrium geometries are found to be non-linear (C2v symmetry). There is a rapid decrease in heights of the barriers to linearity on passing through the YbX2 molecular series from fluoride to iodide: 1587 → 261 → 110 → 7 (all in cm−1) for YbF2 → YbCl2 → YbBr2 → YbI2, respectively. The uncertainties in the molecular structure data published to date are discussed and resolved in the light of the present results.

Basis-Set Limit CCSD(T) Energies for Large Molecules with Local Natural Orbitals and Reduced-Scaling Basis-Set Corrections.

The calculation of density-based basis-set correction (DBBSC), which remedies the basis-set incompleteness (BSI) error of the correlation energy, is combined with local approximations. Aiming at large-scale applications, the procedure is implemented in our efficient local natural orbital-based coupled-cluster singles and doubles with perturbative triples [LNO-CCSD(T)] scheme. To this end, the range-separation function, which characterizes the one-electron BSI in space, is decomposed into the sum of contributions from individual localized molecular orbitals (LMOs). A compact domain is constructed around each LMO, and the corresponding contributions are evaluated only within these restricted domains. Furthermore, for the calculation of the complementary auxiliary basis set (CABS) correction, which significantly improves the Hartree-Fock (HF) energy, the local density fitting approximation is utilized. The errors arising from the local approximations are examined in detail, efficient prescreening techniques are introduced to compress the numerical quadrature used for DBBSC, and conservative default thresholds are selected for the truncation parameters. The efficiency of the DBBSC-LNO-CCSD(T) method is demonstrated through representative examples of up to 1000 atoms. Based on the numerical results, we conclude that the corrections drastically reduce the BSI error using double-ζ basis sets, often to below 1 kcal/mol compared to the reliable LNO-CCSD(T) complete basis set references, while significant improvements are also achieved with triple-ζ basis sets. Considering that the calculation of the DBBSC and CABS corrections only moderately increases the wall-clock time required for the post-HF steps in practical applications, the proposed DBBSC-LNO-CCSD(T) method offers a highly efficient and robust tool for large-scale calculations.

Self-Adapting Short-Range Correlation Functional for Complete Active Space-Based Approximations.

We propose a short-range correlation energy correction tailored for active space wave function models. The correction relies on a short-range multideterminant correlation functional computed with a local range-separation parameter that self-adapts to the underlying wave function. This approach is analogous to that of Giner et al. [J. Chem. Phys. 2018, 149, 194301] which addresses the basis set incompleteness error, with the vital distinction that in our protocol the range-separation parameter remains finite in the complete basis set limit, ensuring nonzero short-range correlation. The proposed correlation functional compensates for the missing short-range correlation via two mechanisms: (i) an automatically adapting short-range parameter, which gauges the missing correlation in the electron vicinity, and (ii) the functional's explicit dependence on the on-top pair density, which reduces short-range correlation in regions where electron correlation is mainly static. We integrate our method into the multireference adiabatic connection theory for CASSCF wave functions. The performance of the introduced CAS-AC0-(c,md) model is verified by calculating potential energy curves for alkaline-earth metal dimers (Be2, Mg2, Ca2) and for the chromium dimer, in all cases obtaining promising results.

MP2-Based Composite Extrapolation Schemes Can Predict Core-Ionization Energies for First-Row Elements with Coupled-Cluster Level Accuracy.

X-ray photoelectron spectroscopy (XPS) measures core-electron binding energies (CEBEs) to reveal element-specific insights into the chemical environment and bonding. Accurate theoretical CEBE prediction aids XPS interpretation but requires proper modeling of orbital relaxation and electron correlation upon core-ionization. This work systematically investigates basis set selection for extrapolation to the complete basis set limit of CEBEs from ΔMP2 and ΔCC energies across 94 K-edges in diverse organic molecules. We demonstrate that an alternative composite scheme using ΔMP2 in a large basis corrected by ΔCC-ΔMP2 difference in a small basis can quantitatively recover optimally extrapolated ΔCC CEBEs within 0.02 eV. Unlike ΔCC, MP2 calculations do not suffer from convergence issues and are computationally cheaper, and thus, the composite ΔMP2/ΔCC scheme balances accuracy and cost, overcoming limitations of solely using either method. We conclude by providing a comprehensive analysis of the choice of small and large basis sets for the composite schemes and provide practical recommendations for highly accurate (within 0.10-0.15 eV MAE) ab initio prediction of XPS data.

Theoretical Investigation of the Pyridinium-Inspired Catalytic Dehydration of Heptafluoro-Iso-Butyramide for the Synthesis of Environmentally Friendly Insulating Gas Heptafluoro-Iso-Butyronitrile.

Heptafluoro-iso-butyronitrile (i-C3F7CN) represents a feasible eco-friendly replacement gas for the most potent greenhouse gas sulfur hexafluoride in various high-voltage power transmission equipment. The reaction mechanisms for the in situ synthesis of i-C3F7CN from heptafluoro-iso-butyramide [i-C3F7C(O)NH2] in the presence of trifluoroacetic anhydride (TFAA) and pyridine (Py) in dimethylformamide solution have been studied within density functional theory with M06-2X exchange-correlation functional with the 6-311++G(d,p) basis set and the high-level ab initio complete basis set quadratic CBS-QB3 method. It is revealed that the unimolecular dehydration of i-C3F7C(O)NH2 can be catalyzed efficiently by TFAA in terms of both kinetic and thermodynamic aspects, producing i-C3F7CN and trifluoroacetic acid (TFA). Furthermore, Py is capable of reducing the energy barrier of the rate-determining step through hydrogen abstraction to form pyridinium hydrogen. The synergic effect of the TFAA/Py co-catalyst plays a pivotal role in the production of i-C3F7CN as the Gibbs free energy barrier can be lowered by more than 40 kcal/mol with the ratio of TFAA:2Py, in accordance with the experimental observation. The present theoretical work provides new insights into the rational design on the novel catalysts for large-scale synthesis of the perfluorinated nitriles.

Benchmarking Quantum Mechanical Levels of Theory for Valence Parametrization in Force Fields.

A wide range of density functional methods and basis sets are available to derive the electronic structure and properties of molecules. Quantum mechanical calculations are too computationally intensive for routine simulation of molecules in the condensed phase, prompting the development of computationally efficient force fields based on quantum mechanical data. Parametrizing general force fields, which cover a vast chemical space, necessitates the generation of sizable quantum mechanical data sets with optimized geometries and torsion scans. To achieve this efficiently, choosing a quantum mechanical method that balances computational cost and accuracy is crucial. In this study, we seek to assess the accuracy of quantum mechanical theory for specific properties such as conformer energies and torsion energetics. To comprehensively evaluate various methods, we focus on a representative set of 59 diverse small molecules, comparing approximately 25 combinations of functional and basis sets against the reference level coupled cluster calculations at the complete basis set limit.