Basis Set Effects Research Articles

Use of caps in the auxiliary basis set formulation of the fragment molecular orbital method.

An auxiliary polarization formulation of the fragment molecular orbital (FMO) method is developed, combining a basis set correction computed for capped isolated fragments with a polarization obtained from uncapped fragments. For a set of organic and inorganic test systems, it is shown that the total energy and atomic charges are accurately reproduced with respect to full unfragmented calculations. It is demonstrated that the method is accurate for computing electronic excited states. The developed approach is applied to rank the isomers of chignolin from experimental NMR data (PDB: 1UAO) according to their relative energy. Contributions of polarization and basis set effects to pair interactions between fragments are elucidated.

The Effective Fragment Molecular Orbital Method: Achieving High Scalability and Accuracy for Large Systems.

The effective fragment molecular orbital (EFMO) method has been developed to predict the total energy of a very large molecular system accurately (with respect to the underlying quantum mechanical method) and efficiently by taking advantage of the locality of strong chemical interactions and employing a two-level hierarchical parallelism. The accuracy of the EFMO method is partly attributed to the accurate and robust intermolecular interaction prediction between distant fragments, in particular, the many-body polarization and dispersion effects, which require the generation of static and dynamic polarizability tensors by solving the coupled perturbed Hartree-Fock (CPHF) and time-dependent HF (TDHF) equations, respectively. Solving the CPHF and TDHF equations is the main EFMO computational bottleneck due to the inefficient (serial) and I/O-intensive implementation of the CPHF and TDHF solvers. In this work, the efficiency and scalability of the EFMO method are significantly improved with a new CPU memory-based implementation for solving the CPHF and TDHF equations that are parallelized by either message passing interface (MPI) or hybrid MPI/OpenMP. The accuracy of the EFMO method is demonstrated for both covalently bonded systems and noncovalently bound molecular clusters by systematically examining the effects of basis sets and a key distance-related cutoff parameter, Rcut. Rcut determines whether a fragment pair (dimer) is treated by the chosen ab initio method or calculated using the effective fragment potential (EFP) method (separated dimers). Decreasing the value of Rcut increases the number of separated (EFP) dimers, thereby decreasing the computational effort. It is demonstrated that excellent accuracy (<1 kcal/mol error per fragment) can be achieved when using a sufficiently large basis set with diffuse functions coupled with a small Rcut value. With the new parallel implementation, the total EFMO wall time is substantially reduced, especially with a high number of MPI ranks. Given a sufficient workload, nearly ideal strong scaling is achieved for the CPHF and TDHF parts of the calculation. For the first time, EFMO calculations with the inclusion of long-range polarization and dispersion interactions on a hydrated mesoporous silica nanoparticle with explicit water solvent molecules (more than 15k atoms) are achieved on a massively parallel supercomputer using nearly 1000 physical nodes. In addition, EFMO calculations on the carbinolamine formation step of an amine-catalyzed aldol reaction at the nanoscale with explicit solvent effects are presented.

Diffusion Monte Carlo method for barrier heights of multiple proton exchanges and complexation energies in small water, ammonia, and hydrogen fluoride clusters.

Proton exchange reactions are of key importance in many processes in water. However, it is nontrivial to achieve reliable barrier heights for multiple proton exchanges and complexation energies in hydrogen-bonded systems theoretically. Performance of the fixed-node diffusion quantum Monte Carlo (FN-DMC) with the single-Slater-Jastrow trial wavefunction on total energies, barrier heights of multiple proton exchanges, and complexation energies of small water, ammonia, and hydrogen fluoride clusters is investigated in this study. Effects of basis sets and those of locality approximation (LA), T-move approximation (T-move), and determinant localization approximation (DLA) schemes in dealing with the nonlocal part of pseudopotentials on FN-DMC results are evaluated. According to our results, diffuse basis functions are important in achieving reliable barrier heights and complexation energies with FN-DMC, although the cardinal number of the basis set is more important than diffuse basis functions on total energies of these systems. Our results also show that the time step bias with DLA and LA is smaller than T-move; however, the time step bias of DMC energies with respect to time steps using the T-move is roughly linear up to 0.06a.u., while this is not the case with LA and DLA. Barrier heights and complexation energies with FN-DMC using these three schemes are always within chemical accuracy. Taking into account the fact that T-move and DLA are typically more stable than LA, FN-DMC calculations with the T-move or DLA scheme and basis sets containing diffuse basis functions are suggested for barrier heights of multiple proton exchanges and complexation energies of hydrogen-bonded clusters.

Impacts of basis sets, solvent models, and NMR methods on the accuracy of 1H and 13C chemical shift calculations for biaryls: a DFT study

Introduction: Biaryls are core structures composed of chiral ligands, organocatalysts, biologically active natural products and biopolymer lignins. In this study, the effects of basis sets, solvent models, and NMR methods on the accuracy of 1H/13C NMR chemical shift calculations for biaryl structures were evaluated. Methods: All calculations were performed using Gaussian09. The GIAO NMR results were observed and extracted using GaussView05. To reduce the systematic error of the calculations, linear regression analysis of the calculated chemical shifts versus the experimental shifts was performed. Results: The tested basis sets showed good 1H/13C results, with CMAE values as low as 0.0425 ppm and 1.09 ppm for 1H and 13C, respectively. The use of solvent models significantly increased the accuracy of the 1H chemical shift calculations. The GIAO method produced more accurate results than did the IGAIM and CSGT methods. Conclusion: This study recommends 6-31G(d,p) and DGDZVP basis sets, IEMPCM and CPCM solvent models, and GIAO NMR methods for the accurate prediction of 1H and 13C chemical shifts for biaryls, assisting in their full structural assignments.

Plane Waves Versus Correlation-Consistent Basis Sets: A Comparison of MP2 Non-Covalent Interaction Energies in the Complete Basis Set Limit.

Second-order Møller-Plesset perturbation theory (MP2) is the most expedient wave function-based method for considering electron correlation in quantum chemical calculations and, as such, provides a cost-effective framework to assess the effects of basis sets on correlation energies, for which the complete basis set (CBS) limit can commonly only be obtained via extrapolation techniques. Software packages providing MP2 energies are commonly based on atom-centered bases with innate issues related to possible basis set superposition errors (BSSE), especially in the case of weakly bonded systems. Here, we present noncovalent interaction energies in the CBS limit, free of BSSE, for 20 dimer systems of the S22 data set obtained via a highly parallelized MP2 implementation in the plane-wave pseudopotential molecular dynamics package CPMD. The specificities related to plane waves for accurate and efficient calculations of gas-phase energies are discussed, and results are compared to the localized (aug-)cc-pV[D,T,Q,5]Z correlation-consistent bases as well as their extrapolated CBS estimates. We find that the BSSE-corrected aug-cc-pV5Z basis can provide MP2 energies highly consistent with the CBS plane wave values with a minimum mean absolute deviation of ∼0.05 kcal/mol without the application of any extrapolation scheme. In addition, we tested the performance of 13 different extrapolation schemes and found that the X-3 expression applied to the (aug-)cc-pVXZ bases provides the smallest deviations against CBS plane wave values if the extrapolation sequence is composed of points D and T, while performs slightly better for TQ and Q5 extrapolations. Also, we propose as a reliable alternative to extrapolate total energies from the DTQ, TQ5, or DTQ5 data points. In spite of the general good agreement between the values obtained from the two types of basis sets, it is noticed that differences between plane waves and (aug-)cc-pVXZ basis sets, extrapolated or not, tend to increase with the number of electrons, thus raising the question of whether these discrepancies could indeed limit the attainable accuracy for localized bases in the limit of large systems.

Experimental and computational studies of 3-(N-morpholinylcarbodithioate)-2-(4-methoxyphenyl)chroman-4-one, a flavanone with potential therapeutical properties

In this paper we are reporting the results obtained regarding 3-(N-morpholinylcarbodithioate)-2-(4-methoxyphenyl)chroman-4-one, mainly by IR and NMR spectroscopy combined with Density Functional Theory calculations. The structural and vibrational characterization of this synthetic flavanone was carried out by performing quantum mechanical calculations in the ground state and by using several hybrid functionals (B3LYP, PBE1PBE, CAM-B3LYP and ωB97X-D) in conjunction with the same basis set, namely 6-311G(d,p). A complete assignment of all the absorption bands present in the vibrational spectrum has been performed.The theoretical 1H and 13C NMR chemical shifts (with respect to TMS) of both isomers of the investigated flavanone were obtained with four DFT-GIAO functionals, i.e. B3LYP, WP04, WC04 and PBE1PBE, in conjunction with the 6-311++G(d,p) and cc-pVDZ basis sets. The values of the theoretical 1H and 13C NMR chemical shifts have been compared with the experimental ones. The effect of different functionals and basis sets on the accuracy and precision in predicting the1H and 13C NMR chemical shifts was also assessed.The chemical potential and oral bioavailability of the studied compound was explored by computing several quantum molecular descriptors that characterize the electronic interactions between a compound and its biological receptor, such as the dipole moment, the energy of frontier molecular orbitals, the gap energy, the electronegativity, the chemical hardness/softness and the electrophilicity index. The druglikeness of the targeted compound was evaluated by using filters known to be efficient in estimating the potential of a molecule to be a bioavailable oral drug.

Decoding Chemical Bonds: Assessment of the Basis Set Effect on Overlap Electron Density Descriptors and Topological Properties in Comparison to QTAIM.

Quantum chemical bonding descriptors based on the total and overlap density can provide valuable information about chemical interactions in different systems. However, these descriptors can be sensitive to the basis set used. To address this, different numerical treatments of electron density have been proposed to reduce the basis set dependency. In this work, we introduce overlap properties (OPs) obtained through numerical treatment of the electron density and present the topology of overlap density (TOP) for the first time. We compare the basis set dependency of numerical OP and TOP descriptors with their quantum theory of atoms in molecules (QTAIM) counterparts, considering the total electron density. Three single (C-C, C-O, and C-F) bonds in ethane, methanol, and fluoromethane and two double (C═C and C═O) bonds in ethene and formaldehyde were analyzed. Diatomic molecules Li-X with X = F, Cl, and Br were also analyzed. Eight parameters, including QTAIM descriptors and OP/TOP descriptors, are used to assess the basis dependency at the ωB97X-D level of theory using 28 basis sets from three classes: Pople, Ahlrichs, and Dunning. The study revealed that the topological overlap electron density properties exhibit comparatively lesser dependence on the basis set compared to their total electron density counterparts. Remarkably, these properties retain their chemical significance even with reduced basis set dependency. Similarly, numerical OP descriptors show less basis set dependency than their QTAIM counterparts. The excess of polarization functions increases charge concentration in the interatomic region and influences both QTAIM and OP descriptors. The basis sets Def2TZVP, 6-31++G(d,p), 6-311++G(d,p), cc-pVDZ, cc-pVTZ, and cc-pVQZ demonstrate reduced variability for the tested bond classes in this study, with particular emphasis on the triple-ζ quality Ahlrichs' basis set. We recommend against using basis sets with numerous polarization functions, such as augmented Dunning's and Ahlrichs' quadruple-ζ.

Irradiation of Plutonium Tributyl Phosphate Complexes by Ionizing Alpha Particles: A Computational Study.

The PUREX solvent extraction process, widely used for recovering uranium and plutonium from spent nuclear fuel, utilizes an organic solvent composed of tributyl phosphate (TBP). The emission of ionizing particles such as alpha particles, resulting from the decay of plutonium, makes the organic solvent vulnerable to degradation. Here, we study the ultrashort time alpha irradiation of tributylphosphate (TBP) and Pu(NO3)4(TBP)2 complex formed in the PUREX process. Electron dynamics is propagated by Real-Time-Dependent Auxiliary Density Functional Theory (RT-TD-ADFT). We investigate the use of previously proposed absorption boundary conditions (ABC) in the molecular orbital space to treat secondary electron emission. Basis set and exchange correlation functional effects with ABC are reported as well as a detailed analysis of the ABC parametrization. Preliminary results on the water molecule and then on TBP show that the phenomenological nature of the ABC parameters necessitates selecting appropriate values for each system under study. Irradiation of free and complexed TBP shows an influence of the ligands on the variation of atomic charges on the femtosecond time scale. An accumulation of atomic charges in the alkyl chains of TBP is observed in the case where the nitrate groups are predominantly irradiated. In addition, we find that the Pu atom regains its electric charge very rapidly after being hit by the projectile, with the coordination sphere serving as an electron reservoir to preserve its formal redox state. This study paves the road toward a full understanding of the degradation of organic extracants employed in the nuclear industry.

Basis Set Effects on the Stabilities and Interaction Energies of Small Amide Molecules Adsorbed on Kaolinite Surface

Adsorptions of small amide molecules, acetamide (AA) and N-methyl-acetamide (NMA) on the surface of kaolinite are investigated in this study. The focus is on the basis set effects towards the stabilities and the interaction energies of the molecules on the Al–O surface. With a fixed B3LYP functional, we increased the size of the basis sets for the single-point calculations, to find the converged interaction energies and obtain the relative stabilities. We found that, under the direct usage of Pople-type and Dunning’s correlation consistent basis sets, it is not possible to achieve the pattern of convergence for the interaction energies and the relative stabilities. Compared to the complete basis set (CBS) extrapolation scheme, the double zeta basis sets deviated the most, in the range of 21 to 27%, while it is from 1 to 7% for the triple zeta basis sets. Based on the results, we suggest using 6-311++G(2df,2pd) or cc-pVQZ for energy-related quantities. Compared to AA, NMA attached more strongly by 0.5 eV on the surface of Al–O.

Accurate Calculation of Isomerization and Conformational Energies of Larger Molecules Using Explicitly Correlated Local Coupled Cluster Methods in Molpro and ORCA.

An overview of the approximations in the explicitly correlated local coupled cluster methods PNO-LCCSD(T)-F12 in Molpro and DLPNO-CCSD(T)F12 in ORCA is given. Options to select the domains of projected atomic orbitals (PAOs), pair natural orbitals (PNOs), and triples natural orbitals (TNOs) in both programs are described and compared in detail. The two programs are applied to compute isomerization and conformational energies of the ISOL24 and ACONFL test sets, where the former is part of the GMTKN55 benchmark suite. Thorough studies of basis set effects are presented for selected systems. These revealed large intramolecular basis set superposition effects that make it practically impossible to reliably determine the complete basis set (CBS) limits without including explicitly correlated terms. The latter strongly reduce the basis set dependence and at the same time also errors caused by the local domain approximations. On the basis of these studies, the PNO-LCCSD(T)-F12 method is applied to determine new reference energies for the above-mentioned benchmark sets. We are confident that our results should agree within a few tenths of a kcal mol-1 with the (unknown) CCSD(T)/CBS values, which therefore allowed us to define computational settings for accurate explicitly correlated local coupled cluster methods with moderate computational effort. With these protocols, especially PNO-LCCSD(T)-F12b/AVTZ', reliable reference values for comprehensive benchmark sets can be generated efficiently. This can significantly advance the development and evaluation of the performance of approximate electronic structure methods, especially improved density functional approximations or machine learning approaches.

Intensity-Borrowing Mechanisms Pertinent to Laser Cooling of Linear Polyatomic Molecules.

A study of the intensity-borrowing mechanisms important to optical cycling transitions in laser-coolable polyatomic molecules arising from non-adiabatic coupling, contributions beyond the Franck-Condon approximation, and Fermi resonances is reported. It has been shown to be necessary to include non-adiabatic coupling to obtain computational accuracy that is sufficient to be useful for laser cooling of molecules. The predicted vibronic branching ratios using perturbation theory based on the non-adiabatic mechanisms have been demonstrated to agree well with those obtained from variational discrete variable representation calculations for representative molecules including CaOH, SrOH, and YbOH. The electron-correlation and basis-set effects on the calculated transition properties, including the vibronic coupling constants, the spin-orbit coupling matrix elements, and the transition dipole moments, and on the calculated branching ratios have been thoroughly studied. The vibronic branching ratios predicted using the present methodologies demonstrate that RaOH is a promising radioactive molecule candidate for laser cooling.

Performance of the COSMO solvation model for photoacidity and basicity in water.

The possibilities and problems to predict excited-state acidities and basicities in water with electronic structure calculations combined with a continuum solvation model are investigated for a test set of photoacids and photobases. Different error sources, like errors in the ground-state values, the excitation energies in solution for the neutral and (de-)protonated species, basis set effects, and contributions beyond implicit solvation are investigated and their contributions to the total error in are discussed. Density functional theory in combination with the conductor like screening model for real solvents and an empirical linear Gibbs free energy relationship are used to predict the ground-state values. For the test set, this approach gives more accurate values for the acids than for the bases. Time-dependent density-functional theory (TD-DFT) and second-order wave function methods in combination with the conductor like screening model are applied to compute excitation energies in water. Some TD-DFT functionals fail for several species to predict correctly the order of the lowest excitations. Where experimental data for absorption maxima in water is available, the implicit solvation model leads with the applied electronic structure methods in most cases for the excitation energies in water to an overestimation for the protonated and to an underestimation for the deprotonated species. The magnitude and sign of the errors depend on the hydrogen bond donating and accepting ability of the solute. We find that for aqueous solution this results generally in an underestimation in the changes from the ground to the excited state for photoacids and an overestimation for photobases.

Investigating the Structural, Electronic, and Topological Properties of [BMIm][Fe(NO)2Cl2] Magnetic Ionic Liquid: Density Functional Theory Approaches

Magnetic ionic liquids (MILs) show clear superiority over conventional ionic liquids suitably nested in many applications, particularly in medicine and drug delivery engineering. The easy way of collecting them using an external magnet and separating them from the reaction mixture is a favorable and unique technique. A magnetic imidazolium-based IL, including iron coordinated with -NO and chloride ligands ([BMIm][Fe(NO)2Cl2]) (BMIm = 1-n-butyl-3-methyl-imidazolium), has been studied using density functional theory. Such dinitrosyl iron compounds are significant as NO-saving sources and carriers because of their longer physiological lifetime compared with molecular NO. The dependability of the calculations was examined and elucidated at three different methods (M06-2X, B3LYP, and B3LYP-D3) to unravel the importance of noncovalent interactions, including dispersion and H-bonding. Also, the effect of a large basis set on different features of this MIL was assessed. This research is a pioneer in theoretically characterizing the type of -NO moiety of this open-shell dinitrosyl iron compound. The complicated structure of the dinitrosyliron unit was determined by the geometrical parameters, stretching frequencies, and magnetic moment calculation. Based on these fingerprint data, the predominant form of two NO's in this MIL is the nitroxyl anion NO-, rather than ṄO or NO+. Unraveling that one of the NO ligands structurally is dangling enhances the application of this MIL as a NO-saving and source compound. Consequently, Fe3+ is identified as the major oxidation state of the iron atom, leading to the MIL with a strong magnetic moment (of 5.22μB).

Toward routine Kohn-Sham inversion using the "Lieb-response" approach.

Kohn-Sham (KS) inversion, in which the effective KS mean-field potential is found for a given density, provides insights into the nature of exact density functional theory (DFT) that can be exploited for the development of density functional approximations. Unfortunately, despite significant and sustained progress in both theory and software libraries, KS inversion remains rather difficult in practice, especially in finite basis sets. The present work presents a KS inversion method, dubbed the "Lieb-response" approach, that naturally works with existing Fock-matrix DFT infrastructure in finite basis sets, is numerically efficient, and directly provides meaningful matrix and energy quantities for pure-state and ensemble systems. Some additional work yields potential. It thus enables the routine inversion of even difficult KS systems, as illustrated in a variety of problems within this work, and provides outputs that can be used for embedding schemes or machine learning of density functional approximations. The effect of finite basis sets on KS inversion is also analyzed and investigated.

Electron Propagator Theory of Vertical Electron Detachment Energies of Anions: Benchmarks and Applications to Nucleotides

A new generation of ab initio electron-propagator self-energy approximations that are free of adjustable parameters is tested on a benchmark set of 55 vertical electron detachment energies of closed-shell anions. Comparisons with older self-energy approximations indicate that several new methods that make the diagonal self-energy approximation in the canonical Hartree-Fock orbital basis provide superior accuracy and computational efficiency. These methods and their acronyms, mean absolute errors (in eV), and arithmetic bottlenecks expressed in terms of occupied (O) and virtual (V) orbitals are the opposite-spin, non-Dyson, diagonal second-order method (os-nD-D2, 0.2, OV2), the approximately renormalized quasiparticle third-order method (Q3+, 0.15, O2V3) and the approximately renormalized, non-Dyson, linear, third-order method (nD-L3+, 0.1, OV4). The Brueckner doubles with triple field operators (BD-T1) nondiagonal electron-propagator method provides such close agreement with coupled-cluster single, double, and perturbative triple replacement total energy differences that it may be used as an alternative means of obtaining standard data. The new methods with diagonal self-energy matrices are the foundation of a composite procedure for estimating basis-set effects. This model produces accurate predictions and clear interpretations based on Dyson orbitals for the photoelectron spectra of the nucleotides found in DNA.

Protonation of serine: conformers, proton affinities and gas-phase basicities at the "gold standard" and beyond.

The potential energy surfaces (PESs) of serine and its protonated counterparts are investigated to determine the structures of the minima. A total of 95 neutral serine, 15 N-(amino-) and 46 O-(carbonyl-)protonated serine conformers are found. Their relative energies, geometries and harmonic vibrational frequencies are determined at the MP2/aug-cc-pVDZ level of theory. To obtain highly accurate thermodynamic values, further computations are performed: the ten conformers with the lowest relative energies from each molecule type (neutral, N- and O-protonated) are further optimized using the explicitly correlated CCSD(T)-F12a/cc-pVDZ-F12 method (for neutral serine, harmonic vibrational frequencies were also computed). In addition, auxiliary corrections were determined: basis-set effects up to CCSD(T)-F12b/cc-pVQZ-F12, electron correlation effects up to CCSDT(Q), core correlation and second-order Douglas-Kroll relativistic effects along with zero-point energy contributions. Two important thermodynamic parameters (at 298.15 K), proton affinity (PA)/gas-phase basicity (GB) are calculated considering the two different protonation sites: 218.05 ± 0.2/209.86 ± 0.6 kcal mol-1 and 205.87 ± 0.2/196.36 ± 0.3 kcal mol-1 for the amino and carbonyl sites, respectively. The uncertainty of the determined values was approximated based on various sources including auxiliary corrections, basis-set effects, harmonic vibrational frequencies.

High-level ab initio mapping of the multiple H-abstraction pathways of the OH + glycine reaction.

We perform a systematic search in the transition-state (TS) and product-channel complex (MIN) regions of the multi-channel OH + glycine → H2O + H2N-CH-COOH (CH)/HN-CH2-COOH (NH)/H2N-CH2-COO (COOH) reactions. Geometry optimizations reveal {7, 3, 3} CH-TS, {2, 2, 2} CH-MIN, {17, 10, 5} NH-TS, {35, 19, 19} NH-MIN, and {6, 5, 5} COOH-TS conformers at the {MP2/3-21G, MP2/aug-cc-pVDZ, CCSD(T)-F12b/aug-cc-pVDZ} levels of theory as well as 2 additional CH-TSs based on chemical intuition. The benchmark relative energies of the TS, MIN, and product conformers are obtained by considering basis set effects up to aug-cc-pVQZ using the explicitly-correlated CCSD(T)-F12b method, post-(T) correlation up to CCSDT(Q), core correlation, scalar relativistic effects, spin-orbit coupling, and zero-point energy corrections. All the CH [ΔEe(ΔH0) = -38.54(-38.61) kcal mol-1], NH [ΔEe(ΔH0) = -16.72(-17.98) kcal mol-1], and COOH [ΔEe = -4.98 kcal mol-1] reactions are exothermic and proceed via shallow, usually negative, classical(adiabatic) barriers of -0.37(-0.95), -1.91(-2.48), and 1.02(-0.57) kcal mol-1, respectively. In the entrance channel MRCI/aug-cc-pVTZ computations reveal several complexes with reactive(non-reactive) arrangements and binding energies of 1.0, 1.6, 3.3, (5.2 and 5.9) kcal mol-1, stabilized by CH⋯OH, NH⋯OH, COOH⋯OH, (OH⋯OC and OH⋯N) hydrogen bonds, respectively.

Relativistic coupled-cluster calculations of RaOH pertinent to spectroscopic detection and laser cooling.

A relativistic coupled-cluster study of the low-lying electronic states in the radium monohydroxide molecule (RaOH), a radioactive polyatomic molecule of interest to laser cooling and to the search of new physics beyond the Standard Model, is reported. The level positions of the A2Π1/2 and C2Σ states have been computed with an accuracy of around 200 cm-1 to facilitate spectroscopic observation of RaOH using laser induced fluorescence spectroscopy, thereby exploiting the systematic convergence of electron-correlation and basis-set effects in relativistic coupled-cluster calculations. The energy level for the B2Δ3/2 state has also been calculated accurately to conclude that the B2Δ3/2 state lies above the A2Π1/2 state. This confirms X2Σ ↔ A2Π1/2 as a promising optical cycling transition for laser cooling RaOH.

Benchmark Ab Initio Determination of the Conformers, Proton Affinities, and Gas-Phase Basicities of Cysteine.

A systematic conformational mapping combined with literature data leads to 85 stable neutral cysteine conformers. The implementation of the same mapping process for the protonated counterparts reveals 21 N-(amino-), 64 O-(carbonyl-), and 37 S-(thiol-)protonated cysteine conformers. Their relative energies and harmonic vibrational frequencies are given at the MP2/aug-cc-pVDZ level of theory. Further benchmark ab initio computations are performed for the 10 lowest-lying neutral and protonated amino acid conformers (for each type) such as CCSD(T)-F12a/cc-pVDZ-F12 geometry optimizations (and frequency computations for cysteine) as well as auxiliary correction computations of the basis set effects up to CCSD(T)-F12b/cc-pVQZ-F12, electron correlation effects up to CCSDT(Q), core correlation effects, second-order Douglass-Kroll relativistic effects, and zero-point energy contributions. Boltzmann-averaged 0 (298.15) K proton affinity and [298.15 K gas-phase basicity] values of cysteine are predicted to be 214.96 (216.39) [208.21], 201.83 (203.55) [194.16], and 193.31 (194.74) [186.40] kcal/mol for N-, O-, and S-protonation, respectively, also considering the previously described auxiliary corrections.

Electron Correlation or Basis Set Quality: How to Obtain Converged and Accurate NMR Shieldings for the Third-Row Elements?

The quality of theoretical NMR shieldings calculated at the quantum-chemical level depends on various theoretical aspects, of which the basis set type and size are among the most important factors. Nevertheless, not much information is available on the basis set effect on theoretical shieldings of the NMR-active nuclei of the third row. Here, we report on the importance of proper basis set selection to obtain accurate and reliable NMR shielding parameters for nuclei from the third row of the periodic table. All calculations were performed on a set of eleven compounds containing the elements Na, Mg, Al, Si, P, S, or Cl. NMR shielding tensors were calculated using the SCF-HF, DFT-B3LYP, and CCSD(T) methods, combined with the Dunning valence aug-cc-pVXZ, core-valence aug-cc-pCVXZ, Jensen polarized-convergent aug-pcSseg-n and Karlsruhe x2c-Def2 basis set families. We also estimated the complete basis set limit (CBS) values of the NMR parameters. Widely scattered nuclear shieldings were observed for the Dunning polarized-valence basis set, which provides irregular convergence. We show that the use of Dunning core-valence or Jensen basis sets effectively reduces the scatter of theoretical NMR results and leads to their exponential-like convergence to CBS. We also assessed the effect of vibrational, temperature, and relativistic corrections on the predicted shieldings. For systems with single bonds, all corrections are relatively small, amounting to less than 4% of the CCSD(T)/CBS value. Vibrational and temperature corrections were less reliable for H3PO and HSiCH due to the high anharmonicity of the molecules. An abnormally high relativistic correction was observed for phosphorus in PN, reaching ~20% of the CCSD(T)/CBS value, while the correction was less than 7% for other tested molecules.