Large Basis Sets Research Articles

Study of single electron capture in O6+ + He collisions

Research on electron capture (EC) process are undoubtedly helpful for maturing theoretical models on ion-induced collision especially for low-energy region. In this work, a two-active-electron semiclassical asymptotic-state close-coupling method was used to calculate the total and l-solved state-selective single EC cross sections of O6+ + He collisions in the energy range of 0.3–100 keV u−1, accompanied with experimental measurements in the energy range of 2.63–37.5 keV u−1 with an uncertainty of 11% in good agreement. Above 4.5 keV u−1, the state-selective cross section of n = 5 was reported experimentally for the first time. Calculations with multiple theoretical methods were gathered and compared with present calculations. The importance of two-active-electrons correlation and large basis sets in theoretical calculations was found, and discrepancies between previous theoretical and experimental results can be explained by the present results.

Accuracy of Different Electronic Basis Set Families for Anharmonic Molecular Vibrations: A Comprehensive Benchmark Study.

In this work, the accuracy and convergence of different electronic basis set families for the computation of anharmonic molecular vibrational spectroscopic calculations are benchmarked. A series of 39 different basis sets from different families following their hierarchy are assessed on VSCF and VSCF-PT2 algorithms with commonly used MP2 and DFT based B3LYP-D potentials for a set of molecular systems. Such an effort has been validated in a previous work ( J. Phys. Chem. A 2020, 124, 9203-9221) with split-valence basis sets for fundamentals and intensities. Here, fundamental transitions, vibrationally excited states, and intensities are compared with the experimental data to estimate the accuracy for a series of Jensen, Dunning, Calendar, Karlsruhe, and Sapporo basis set families. The convergence of basis sets are also compared with the large ANO basis set. Comprehensive statistical error analysis in terms of accuracy and precision was carried out to assess the performance of each basis set. It is observed that the improvement for the calculated harmonic and anharmonic values from the smaller basis sets to the medium (i.e., triple-ξ) is considerable. Beyond this, from medium to large basis sets, the convergence is slow and mostly posits nearly converged values. Basis sets with and without diffuse functions offer characteristically different accuracies and convergence patterns. Finally, recommendations are given on the choice of basis set chosen as black-box which can balance between accuracy and computational time, estimation of the errors, and their selections especially for large molecules.

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.

Barrier Heights for Diels-Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules.

Theoretical characterization of reactions of complex molecules depends on providing consistent accuracy for the relative energies of intermediates and transition states. Here we employ the DLPNO-CCSD(T) method with core-valence correlation, large basis sets, and extrapolation to the CBS limit to provide benchmark values for Diels-Alder transition states leading to competitive strained pentacyclic adducts. We then used those benchmarks to test a diverse set of wave function and density functional methods for the absolute and relative barrier heights of these transition states. Our results show that only a few of the tested density functionals can predict the absolute barrier heights satisfactorily, although relative barrier heights are more accurate. The most accurate functionals tested are ωB97M-V, M11plus, ωB97X-V, PBE-D3(0), M11, and MN15 with MUDs from best estimates less than 3.0 kcal. These findings can guide selection of density functionals for future studies of crowded, strained transition states of large molecules.

Do Planar Tetracoordinate Fluorine Atoms Exist? Revisiting a Theoretical Prediction.

We re-examined the existence of planar tetracoordinate F (ptF) atoms, which was proposed recently by using high-level ab initio methods such as coupled-cluster singles and doubles with perturbative triples (CCSD(T)) with large basis sets. Our calculations indicate that the planar structures of FIn4+ (D4h), FTl4+ (D4h), FGaIn3+ (C2V), FIn2Tl2+ (D2h), FIn3Tl+ (C2V), and FInTl3+ (C2V) are not the minimum energy states; by contrast, they are transition states. Density functional theory calculations overestimate the size of the cavity formed by the four peripheral atoms, leading to erroneous conclusions regarding the existence of ptF atoms. Our analysis suggests that the preference for non-planar structures in the six cations studied is not due to the pseudo Jahn-Teller effect. Additionally, spin-orbit coupling does not alter the main conclusion that the ptF atom does not exist. If sufficiently large cavity formation by group 13 elements to accommodate the central F- ion is guaranteed, then the existence of ptF atoms is plausible.

Electron/Hole Mobilities of Periodic DNA and Nucleobase Structures from Large-Scale DFT Calculations.

Electron/hole transfer mechanisms in DNA and polynucleotide structures continue to garner considerable interest as emerging charge-transport systems and molecular electronics. To shed mechanistic insight into these electronic properties, we carried out large-scale density functional theory (DFT) calculations (up to 650 atoms) to systematically analyze the structural and electron/hole transport properties of fully periodic single- and double-stranded DNA. We examined the performance of various exchange-correlation functionals (LDA, BLYP, B3LYP, and B3LYP-D) and found that single-stranded thymine (T) and cytosine (C) are predominantly hole conductors, whereas single-stranded adenine (A) and guanine (G) are better electron conductors. For double-stranded DNA structures, the periodic A-T and G-C electronic band structures undergo a significant renormalization, which causes hole transport to only occur on the A and G nucleobases. Our calculations (1) provide new benchmarks for periodic nucleobase structures using dispersion-corrected hybrid functionals with large basis sets and (2) highlight the importance of dispersion effects for obtaining accurate geometries and electron/hole mobilities in these extended systems.

Spectroscopic Properties of the Alkali-Krypton Diatomic M-Kr (M = Rb, Cs, and Fr) van der Waals Systems Including the Spin-Orbit Coupling.

Using an ab initio approach based on pseudopotential technique, pair potential approach, core polarization potentials, and large Gaussian basis sets, we investigate interaction of heavy alkali-krypton diatomic M-Kr (M = Rb, Cs, and Fr) van der Waals dimers. In this context, the core-core interactions for M+-Kr (M = Rb, Cs, and Fr) are calculated at coupled-cluster single and double excitation (CCSD) level and included in the total potential energy. Therefore, the potential energy curves are performed for 14 electronic states: eight of 2Σ+ symmetry, four of 2Π symmetry, and two of 2Δ symmetry. Furthermore, for each M-Kr dimer, the spin-orbit coupling has been considered for the B2Σ+, A2Π, 32Σ+, 22Π, 52Σ+, 32Π, and 12Δ states. In addition, the transition dipole moment has been determined, including the spin-orbit effect using the rotational matrix issued from the spin-orbit potential energy calculations.

Band structures and Z2 invariants of two-dimensional transition metal dichalcogenide monolayers from fully relativistic Dirac-Kohn-Sham theory using Gaussian-type orbitals

Two-dimensional (2D) materials exhibit a wide range of remarkable phenomena, many of which owe their existence to the relativistic spin-orbit coupling (SOC) effects. To understand and predict properties of materials containing heavy elements, such as the transition-metal dichalcogenides (TMDs), relativistic effects must be taken into account in first-principles calculations. We present an all-electron method based on the four-component Dirac Hamiltonian and Gaussian-type orbitals (GTOs) that overcomes complications associated with linear dependencies and ill-conditioned matrices that arise when diffuse functions are included in the basis. Until now, there has been no systematic study of the convergence of GTO basis sets for periodic solids either at the nonrelativistic or the relativistic level. Here we provide such a study of relativistic band structures of the 2D TMDs in the hexagonal (2H), tetragonal (1T), and distorted tetragonal (1T') structures, along with a discussion of their SOC-driven properties (Rashba splitting and $\mathbb{Z}_2$ topological invariants). We demonstrate the viability of our approach even when large basis sets with multiple basis functions involving various valence orbitals (denoted triple- and quadruple-$\zeta$) are used in the relativistic regime. Our method does not require the use of pseudopotentials and provides access to all electronic states within the same framework. Our study paves the way for direct studies of material properties, such as the parameters in spin Hamiltonians, that depend heavily on the electron density near atomic nuclei where relativistic and SOC effects are the strongest.

Single-Point Extrapolation to the Complete Basis Set Limit through Deep Learning.

Machine learning (ML) offers an attractive method for making predictions about molecular systems while circumventing the need to run expensive electronic structure calculations. Once trained on ab initio data, the promise of ML is to deliver accurate predictions of molecular properties that were previously computationally infeasible. In this work, we develop and train a graph neural network model to correct the basis set incompleteness error (BSIE) between a small and large basis set at the RHF and B3LYP levels of theory. Our results show that, when compared to fitting to the total potential, an ML model fitted to correct the BSIE is better at generalizing to systems not seen during training. We test this ability by training on single molecules while evaluating on molecular complexes. We also show that ensemble models yield better behaved potentials in situations where the training data is insufficient. However, even when only fitting to the BSIE, acceptable performance is only achieved when the training data sufficiently resemble the systems one wants to make predictions on. The test error of the final model trained to predict the difference between the cc-pVDZ and cc-pV5Z potential is 0.184 kcal/mol for the B3LYP density functional, and the ensemble model accurately reproduces the large basis set interaction energy curves on the S66x8 dataset.

Spectroscopic constants and transition properties on the singlet states of van der Waals molecules Cd-RG(RG = He,Ne,Ar,Kr,Xe,Rn)

By using CCSD(T) and EOM-CCSD methods together with quasirelativistic energy-consistent small-core pseudopotentials and large atom-centered basis sets as well as bond functions, the potential energy curves (PECs) for the ground state and several low-lying singlet excited states of the van der Waals molecular systems between cadmium atom interacting with RG atoms (RG = He, Ne, Ar, Kr, Xe and Rn) are obtained. The dispersion coefficients of ground state for Cd-RG have been computed. And the spectroscopic constants of the bound states of Cd-RG molecules have been calculated, the spectroscopic constants of ground state and C1Π state of Cd-RG complexes are in reasonable agreement with the available theoretical and experimental results; the vertical excitation energies of singlet low-lying excited states are also obtained. And the transition dipole moments (TDMs) of (3)1Σ+-X1Σ+ and (4)1Σ+-X1Σ+ transitions are discussed, which would be helpful to understand the transition properties of Cd-RG complex. Furthermore, frequencies of vibrational transitions, rotational constants, Franck-Condon factors (FCFs) of C1Π-X1Σ+ transition and oscillator strengths of Cd-RG have also been acquired. The present work would be of value to understand on the electronically excited states of Cd-RG molecule, especially the electronic structure and spectroscopic characteristics of the singlet excited states.

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).

Adaptive basis sets for practical quantum computing

AbstractElectronic structure calculations on small systems such as H2, H2O, LiH, and BeH2 with chemical accuracy are still a challenge for the current generation of noisy intermediate‐scale quantum (NISQ) devices. One of the reasons is that due to the device limitations, only minimal basis sets are commonly applied in quantum chemical calculations, which allows one to keep the number of qubits employed in the calculations at a minimum. However, the use of minimal basis sets leads to very large errors in the computed molecular energies as well as potential energy surface shapes. One way to increase the accuracy of electronic structure calculations is through the development of small basis sets better suited for quantum computing. In this work, we show that the use of adaptive basis sets, in which exponents and contraction coefficients depend on molecular structure, provides an easy way to dramatically improve the accuracy of quantum chemical calculations without the need to increase the basis set size and thus the number of qubits utilized in quantum circuits. As a proof of principle, we optimize an adaptive minimal basis set for quantum computing calculations on an H2 molecule, in which exponents and contraction coefficients depend on the HH distance, and apply it to the generation of H2 potential energy surface on IBM‐Q quantum devices. The adaptive minimal basis set reaches the accuracy of the double‐zeta basis sets, thus allowing one to perform double‐zeta quality calculations on quantum devices without the need to utilize twice as many qubits in simulations. This approach can be extended to other molecular systems and larger basis sets in a straightforward manner.

On the computation of frequency‐dependent molecular magnetizabilities via dynamical charge and current electron densities

In the computation of molecular dynamic magnetizabilities and magnetic dipole moments, three different reference points are required: (i) origin of coordinate system, (ii) origin of vector potential , and (iii) origin of multipole expansion. This study shows that methods relying on continuous translation of origin of the current density induced by optical magnetic fields provide an effective solution to the problem of choices (i) and (ii), in that they yield origin independent within the algebraic approximation, for any basis set. Frequency-dependent magnetizabilities are also invariant with respect to (iii), as a consequence of symmetry, for a number of molecular point groups. In molecules of lower symmetries, computed magnetizabilities depend on origin of the multipole expansion. Large basis set computations carried out for water, ammonia, methane, ethane, ethylene, boranylborane, and hydroxilamine, at the DFT level, have been reported to document these statements. A comparison is made for results obtained within the conventional common origin approach for static magnetic field. Sum rules for invariance of computed properties are discussed. Representations of streamlines and stagnation graphs of dynamical current density vector field induced in the water molecule by monochromatic waves of four frequencies are displayed.

The molecular level study of the fate of the CH3CH2C(O)OCH(O)CH3 radical derived from ethyl propionate

ABSTRACT A quantum chemical study has been presented on the decomposition of CH3CH2C(O)OCH(O • )CH3 which is derived from ethyl propionate (CH3CH2C(O)OCH2CH3) using the M06-2X/6-31 + G(d,p) level of theory. The thermal decomposition of CH3CH2C(O)OCH(O • )CH3 is essential to understand the chemistry of combustion of ethyl propionate. Here, the decomposition and oxidative pathways, bond fission and alpha ester rearrangement of CH3CH2C(O)OCH(O • )CH3 have been explored. We have obtained transition states for the different pathways and further verified each transition state by performing intrinsic reaction coordinate (IRC) calculations. The density of state spectra (DOS) was calculated using GaussSum software. The single-point energy calculations are performed at the same function but using larger basis sets such as 6-311++G(d,p) and 6-311++G(3df,2p). We have shown all stationary points and transition states involved in reaction pathways on the potential energy surface (PES) diagram and also discussed the thermochemistry of each reaction pathway. The thermal rate constants of various channels in the decomposition of CH3CH2C(O)OCH(O • )CH3 are determined using the Conventional Transition State Theory (CTST) in the temperature range of 250–450 K and 1atm. From PES, thermochemistry and kinetics analysis, we found that α-ester rearrangement produces propionic acid, which is dominant over the oxidative pathway for the decomposition of CH3CH2C(O)OCH(O • )CH3.

Theoretical Investigations on the Interactions of Urea with Hydroxyl and Non-Hydroxyl Hydroxyapatite Surface

We performed an investigation on urea interacting with hydroxyapatite (HA). The oxygen atoms on HA are either left alone or added with hydrogen to create hydroxyl to resemble the HA surface. Using B3LYP and 3 different basis sets, it was found that urea was able to interact positively with either hydroxyl or non-hydroxyl surface of HA. The Gaussian 09 and Multiwfn software were employed to conduct the calculations. The most favorable interaction has interaction energy of –1.36 eV, which was obtained with the 2 largest basis sets considered, on the pure hydroxyl surface. From the topology analysis on electron density and the non-covalent interaction analysis, it was found that the main attractions between urea and HA were due to the carbonyl oxygen and hydrogen of urea, and hydrogen, oxygen, and calcium on the HA surface. The bond length of newly bonded atoms ranges from 1.62 to 5.18 Å, whereas the energy gap has range between 0.46 to 1.14 eV. All the analysis performed in this study agreed with the results obtained in the formation of favorable interactions and complement previous experimental results that HA can bond with urea molecule. HIGHLIGHTS First known attempt to compare hydrogen-terminated and non-terminated surface of HA in urea adsorption The atoms involved in the adsorption were identified, and electronic structure of the possible combination was analysed and studied using topology and non-covalent interaction analysis Urea attached to both surfaces are stable, with negative interaction energy, confirming experiments’ results that urea can be adsorbed to HA GRAPHICAL ABSTRACT

DFT and TD-DFT study of hydrogen bonded complexes of aspartic acid and n water (n = 1 and 2)

Hydrogen bonds (HB) influence the conformational preferences of biomolecules and their optical and electronic properties. The directional interaction of molecules of water can be a prototype to understand the effects of HBs on biomolecules. Among the neurotransmitters (NT), L-aspartic acid (ASP) stands out due to its importance in health and as a precursor of several biomolecules. As it presents different functional groups and readily forms inter- and intramolecular HBs, ASP can be considered a prototype for understanding the behavior of NTs when interacting by HB with other substances. Although several theoretical studies have been performed in the past on isolated ASP and its formed complexes with water, both in gas and liquid phases, using DFT and TD-DFT formalisms, these works did not perform large basis set calculations or study electronic transitions of ASP-water complexes. We investigated the HB interactions in complexes of ASP and water molecules. The results show that the interactions between the carboxylic groups of ASP with water molecules, forming cyclic structures with two HBs, lead to more stable and less polar complexes than other conformers formed between water and the NH2 group. It was observed that there is a relationship between the deviation in the UV-Vis absorption band of the ASP and the interactions of water with the HOMO and LUMO orbitals with the stabilization/destabilization of the S1 state to the S0 of the complexes. However, in some cases, such as 1:1 complex ASP-W2, this analysis may be inaccurate due to small changes in ΔE. We studied the landscapes of the ground state surface of different conformers of isolated L-ASP and the L-ASP-(H2O)n complexes (n = 1 and 2) using the DFT formalism, with the B3LYP functional, and six different basis sets: 6-31 + + G(d,p), 6-311 + + G(d,p), D95 + + (d,p), D95V + + (d,p), cc-pVDZ, and, cc-pVTZ basis sets. The cc-pVTZ basis set provides the minimum energy of all conformers, and therefore, we performed the analysis with this basis set. We evaluated the stabilization of the ASP and complexes using the minimum ground state energy, corrected by the zero point energy and the interaction energy between the ASP and the water molecules. We also calculated the vertical electronic transitions S1 ← S0, and their properties using the TD-DFT formalism at B3LYP/cc-pVTZ level with the optimized geometries for S0 state with the same basis set. For the analysis of the vertical transitions of isolated ASP and the ASP-(H2O)n complexes, we calculated the electrostatic energy in the S0 and S1 states. We performed the calculations with the Gaussian 09 software package. We used the VMD software package to visualize the geometries and shapes of the molecule and complexes.

Rate coefficients for rotational state-to-state transitions in H2O + H2O collisions for cometary and planetary applications, as predicted by mixed quantum-classical theory

Aims. We present new calculations of collision cross sections for state-to-state transitions between the rotational states in an H2O + H2O system, which are used to generate a new database of collisional rate coefficients for cometary and planetary applications. Methods. Calculations were carried out using a mixed quantum-classical theory approach that is implemented in the code MQCT. The large basis set of rotational states used in these calculations permits us to predict thermally averaged cross sections for 441 transitions in para- and ortho-H2O in a broad range of temperatures. Results. It is found that all state-to-state transitions in the H2O + H2O system split into two well-defined groups, one with higher cross-section values and lower energy transfer, which corresponds to the dipole-dipole driven processes. The other group has smaller cross sections and higher energy transfer, driven by higher-order interaction terms. We present a detailed analysis of the theoretical error bars, and we symmetrized the state-to-state transition matrixes to ensure that excitation and quenching processes for each transition satisfy the principle of microscopic reversibility. We also compare our results with other data available from the literature for H2O + H2O collisions.

Model Chemistry Recommendations for Scaled Harmonic Frequency Calculations: A Benchmark Study

Despite the widespread popularity of scaled harmonic frequency calculations to predict experimental fundamental frequencies in chemistry, sparse benchmarking is available to guide users on the appropriate level of theory and basis set choices (model chemistry) or deep understanding of expected errors. An updated assessment of the best approach for scaling to minimize errors is also overdue. Here, we assess the performance of over 600 popular, contemporary, and robust model chemistries in the calculation of scaled harmonic frequencies, evaluating different scaling factor types and their implications in the scaled harmonic frequencies and model chemistry performance. We can summarize our results into three main findings: (1) Using model-chemistry-specific scaling factors optimized for three different frequency regions (low (<1,000 cm-1), mid (1,000-2,000 cm-1), and high (>2,000 cm-1)) results in substantial improvements in the agreement between the scaled harmonic and experimental frequencies compared to other choices. (2) Larger basis sets and more robust levels of theory generally lead to superior performance; however, the particular model chemistry choice matters and poor choices lead to significantly reduced accuracies. (3) Outliers are expected in routine calculations regardless of the model chemistry choice. Our benchmarking results here do not consider the intensity of vibrational transitions; however, we draw upon previous benchmarking results for dipole moments that highlight the importance of diffuse functions (i.e., augmented basis sets) in high-quality intensity predictions. In terms of specific recommendations, overall, the highest accuracy model chemistries are double-hybrid density functional approximations with a non-Pople augmented triple-ζ basis set, which can produce median frequency errors down to 7.6 cm-1 (DSD-PBEP86/def2-TZVPD), which is very close to the error in the harmonic approximation, i.e., the anharmonicity error. Double-ζ basis sets should not be used with double-hybrid functionals as there is no improvement compared to hybrid functional results (unlike for double-hybrid triple-ζ model chemistries). Note that 6-311G* and 6-311+G* basis sets perform like a double-ζ basis set for vibrational frequencies. After scaling, all studied hybrid functionals with non-Pople triple-ζ basis sets will produce median errors of less than 15 cm-1, with the best result of 9.9 cm-1 with B97-1/def2-TZVPD. Appropriate matching of double-ζ basis sets with hybrid functionals can produce high-quality results, but the precise choice of functional and basis set is more important. The B97-1, TPSS0-D3(BJ), or ωB97X-D hybrid density functionals with 6-31G*, pc-1, or pcseg-1 are recommended for fast routine calculations, all delivering median errors of 11-12 cm-1. Note that dispersion corrections are not easily available for B97-1; given its strong performance here, we recommend these be added to major programs in coming updates.

Characterization of competing halogen-bonding and hydrogen-bonding motifs in the acetonitrile/hydrogen iodide dimer

Three different C3v configurations of the CH3CN/HI dimer have been characterized using MP2 and CCSD(T) methods with large correlation consistent basis sets. All three stationary points are minima. The hydrogen bonded CH3CN⋯HI configuration is the global minimum (GM) with an electronic dissociation energy exceeding 4 kcal mol−1 near the CCSD(T) complete basis set (CBS) limit. A strongly bound halogen-bonded form of the dimer, CH3CN⋯IH, lies within 0.9 kcal mol−1 of the GM according to CCSD(T) electronic energies extrapolated to the CBS limit. The energetic separation between the two minima decreases by approximately 0.1 kcal mol−1 at all levels of theory when the harmonic zero-point vibrational energies are included. A third minimum was identified in which iodine interacts with the hydrogens of the methyl group (HI⋯CH3CN). This minimum is significantly higher in energy than the GM, almost within 1 kcal mol−1 of the dissociation limit. The GM has been previously identified via matrix isolation infrared spectroscopy. The energetics, vibrational frequencies, and infrared intensities computed here corroborate the tentative assignment of a second feature in the HI stretching region of the experimental infrared spectrum to the halogen-bonded configuration.

Hydrogen-Atom Electronic Basis Sets for Multicomponent Quantum Chemistry.

Multicomponent methods are a conceptually simple way to include nuclear quantum effects into quantum chemistry calculations. In multicomponent methods, the electronic molecular orbitals are described using the linear combination of atomic orbitals approximation. This requires the selection of a one-particle electronic basis set which, in practice, is commonly a correlation-consistent basis set. In multicomponent method studies, it has been demonstrated that large electronic basis sets are required for quantum hydrogen nuclei to accurately describe electron-nuclear correlation. However, as we show in this study, much of the need for large electronic basis sets is due to the correlation-consistent electronic basis sets not being optimized to describe nuclear properties and electron-nuclear correlation. Herein, we introduce a series of correlation-consistent electronic basis sets for hydrogen atoms called cc-pVnZ-mc with additional basis functions optimized to reproduce multicomponent density functional theory protonic densities. These new electronic basis sets are shown to yield better protonic densities with fewer electronic basis functions than the standard correlation-consistent basis sets and reproduce other protonic properties such as proton affinities and protonic excitation energies, even though they were not optimized for these purposes. The cc-pVnZ-mc basis sets should enable multicomponent many-body calculations on larger systems due to the improved computational efficiency they provide for a given level of accuracy.