Exploring the Tl 2 H 2 potential energy surface: A comparative analysis with group 13 systems and experiment.

Thallium chemistry is experiencing unprecedented importance. Therefore, it is valuable to characterize some of the simplest thallium compounds. Stationary points along the singlet and triplet Tl 2 H 2 potential energy surface have been characterized. Stationary point geometries were optimized with the CCSD(T)/aug-cc-pwCVQZ-PP method. Harmonic vibrational frequencies were computed at the same level of theory while anharmonic vibrational frequencies were computed at the CCSD(T)/aug-cc-pwCVTZ-PP level of theory. Final energetics were obtained with the CCSDT(Q) method. Basis sets up to augmented quintuple-zeta cardinality (aug-cc-pwCV5Z-PP) were employed to obtain energetics in order to extrapolate to the complete basis set limits using the focal point approach. Zero-point vibrational energy corrections were appended to the extrapolated energies in order to determine relative energies at 0 K. It was found that the planar dibridged isomer lies lowest in energy while the linear structure lies highest in energy. The results were compared to other group 13 M 2 H 2 (M = B, Al, Ga, In, and Tl) theoretical studies and some interesting variations are found. With respect to experiment, incompatibilities exist.

A wealth of structures for the Ge2H2+ radical cation: comparison of theory and experiment.

Five structures of Ge2H2 and Ge2H2+ are investigated in this study. Optimized geometries at the CCSD(T)/cc-pwCVQZ-PP level of theory were obtained. Focal point analyses were performed on these optimized geometries to determine relative energies using the CCSD(T) method with polarized basis sets up to quintuple-zeta. Energy corrections include full T and pertubative (Q) coupled-cluster effects plus anharmonic corrections to the zero-point vibrational energy. Relative ordering in energy from lowest to highest of the five Ge2H2+ structures is butterfly, germylidene, monobridged, trans, then linear. In neutral Ge2H2, the monobridged structure lies lower in energy than the germylidene structure. Fundamental vibrational frequencies and IR intensities were computed for the minima at the CCSD(T)/cc-pwCVTZ-PP level of theory to compare with experimental research. Partial atomic charges and natural bonding orbital analyses indicated that the positive charge of Ge2H2+ is contained in the region of the Ge-Ge bond.

Comparative Study of Neutral and Cationic Sn2H2: Toward Laboratory Detection of the Cation.

Group 14 M2H2 isomers (M = Si, Ge, Sn, and Pb) have attracted interest due to their radically differing electronic structures from acetylene. To better understand the Sn-H interactions of the neutral and cationic Sn2H2 structures, we present the most rigorous study of these systems to date. CCSD(T)/cc-pwCVTZ harmonic frequencies are presented as the first predictions for the neutral and cationic species to date. CCSDT(Q)/CBS relative energies are reported using the focal point approach, confirming the butterfly isomer as the global minimum on the potential energy surface for both the neutral and cationic species. In all, there exist 7 minima and 15 transition states. NBO analysis is also performed to elucidate the changes in bond order going from neutral to cation across all isomers of Sn2H2. Our results provide insights into the important Sn-H interaction and provide guidance for future work that may detect Sn2H2+ in the laboratory for the first time.

MolSym: A Python package for handling symmetry in molecular quantum chemistry.

A consideration of the point group symmetry of molecules is often advantageous from a computational efficiency standpoint and sometimes necessary for the correct treatment of chemical physics problems. Many modern electronic structure software packages include a treatment of symmetry, but these are sometimes incomplete or unusable outside of that program's environment. Therefore, we have developed the MolSym package for handling molecular symmetry and its associated functionalities to provide a platform for including symmetry in the implementation and development of other methods. Features include point group detection, molecule symmetrization, arbitrary generation of symmetry element sets and character tables, and symmetry adapted linear combinations of real spherical harmonic basis functions, Cartesian displacement coordinates, and internal coordinates. We present some of the advantages of using molecular symmetry as achieved by MolSym, particularly with respect to Hartree-Fock theory, and the reduction of finite difference displacements in gradient/Hessian computations. This package is designed to be easily integrated into other software development efforts and may be extended to further symmetry applications.

Accurate and efficient open-source implementation of domain-based local pair natural orbital (DLPNO) coupled-cluster theory using a t1-transformed Hamiltonian.

We present an efficient, open-source formulation for coupled-cluster theory through perturbative triples with domain-based local pair natural orbitals [DLPNO-CCSD(T)]. Similar to the implementation of the DLPNO-CCSD(T) method found in the ORCA package, the most expensive integral generation and contraction steps associated with the CCSD(T) method are linear-scaling. In this work, we show that the t1-transformed Hamiltonian allows for a less complex algorithm when evaluating the local CCSD(T) energy without compromising efficiency or accuracy. Our algorithm yields sub-kJ mol-1 deviations for relative energies when compared with canonical CCSD(T), with typical errors being on the order of 0.1 kcal mol-1, using our TightPNO parameters. We extensively tested and optimized our algorithm and parameters for non-covalent interactions, which have been the most difficult interaction to model for orbital (PNO)-based methods historically. To highlight the capabilities of our code, we tested it on large water clusters, as well as insulin (787 atoms).

Simulation of the VUV Absorption Spectra of Oxygenates and Hydrocarbons: A Joint Theoretical-Experimental Study.

Vacuum UV absorption spectroscopy is regularly used to provide unambiguous identification of a target species, insight into the electronic structure of molecules, and quantitative species concentrations. As molecules of interest have become more complex, theoretical spectra have been used in tandem with laboratory spectroscopic analysis or as a replacement when experimental data is unavailable. However, it is difficult to determine which theoretical methodologies can best simulate experiment. This study examined the performance of EOM-CCSD and 10 TD-DFT functionals (B3LYP, BH&HLYP, BMK, CAM-B3LYP, HSE, M06-2X, M11, PBE0, ωB97X-D, and X3LYP) to produce reliable vacuum UV absorption spectra for 19 small oxygenates and hydrocarbons using vertical excitation energies. The simulated spectra were analyzed against experiment using both a qualitative analysis and quantitative metrics, including cosine similarity, relative integral change, mean signed error, and mean absolute error. Based on our ranking system, it was determined that M06-2X was consistently the top performing TD-DFT method with BMK, CAM-B3LYP, and ωB97X-D also producing reliable spectra for these small combustion species.

Comparison of multifidelity machine learning models for potential energy surfaces.

Multifidelity modeling is a technique for fusing the information from two or more datasets into one model. It is particularly advantageous when one dataset contains few accurate results and the other contains many less accurate results. Within the context of modeling potential energy surfaces, the low-fidelity dataset can be made up of a large number of inexpensive energy computations that provide adequate coverage of the N-dimensional space spanned by the molecular internal coordinates. The high-fidelity dataset can provide fewer but more accurate electronic energies for the molecule in question. Here, we compare the performance of several neural network-based approaches to multifidelity modeling. We show that the four methods (dual, Δ-learning, weight transfer, and Meng-Karniadakis neural networks) outperform a traditional implementation of a neural network, given the same amount of training data. We also show that the Δ-learning approach is the most practical and tends to provide the most accurate model.

Enthalpies of formation for Criegee intermediates: A correlation energy convergence study.

Criegee intermediates, formed from the ozonolysis of alkenes, are known to have a role in atmospheric chemistry, including the modulation of the oxidizing capacity of the troposphere. Although studies have been conducted since their discovery, the synthesis of these species in the laboratory has ushered in a new wave of investigations of these structures, both theoretically and experimentally. In some of these theoretical studies, high-order corrections for correlation energy are included to account for the mid multi-reference character found in these systems. Many of these studies include a focus on kinetics; therefore, the calculated energies should be accurate (<1 kcal/mol in error). In this research, we compute the enthalpies of formation for a small set of Criegee intermediates, including higher-order coupled cluster corrections for correlation energy up to coupled cluster with perturbative quintuple excitations. The enthalpies of formation for formaldehyde oxide, anti-acetaldehyde oxide, syn-acetaldehyde oxide, and acetone oxide are presented at 0 K as 26.5, 15.6, 12.2, and 0.1 kcal mol-1, respectively. Additionally, we do not recommend the coupled cluster with perturbative quadruple excitations [CCSDT(Q)] energy correction, as it is approximately twice as large as that of the coupled cluster with full quadruple excitations (CCSDTQ). Half of the CCSDT(Q) energy correction may be included as a reliable, cost-effective estimation of CCSDTQ energies for Criegee intermediates.

Toward the Observation of the Tin and Lead Analogs of Formaldehyde.

Heavy aldehyde and ketone analogues, R2X═O (X = Si, Ge, Sn, or Pb), differ from their R2C═O counterparts due to their greater tendency to oligeramize as the X═O bond polarity increases as one goes down the periodic table. To date, H2Sn═O and H2Pb═O have eluded experimental detection. Herein we present the most rigorous theoretical study to date on these structures, providing CCSD(T)/pwCVTZ fundamental frequencies computed on CCSD(T)/CBS optimized structures for the H2X═O (X = Sn, Pb) potential energy surface. The focal point approach is employed to produce the CCSDTQ/CBS relative energies. For the Sn and Pb structures, the carbene-like cis-HXOH was the global minima, with the trans species being less than 0.6 and 1.1 kcal mol-1 above the cis structures, respectively. The formaldehyde-like H2X═O structure is in an energy well of at least 34.8 and 25.4 kcal mol-1 for Sn and Pb, respectively. Our results provide guidance for future work that may detect H2Sn═O or H2Pb═O for the first time.

Group 15 and 16 Nitrene-Like Pnictinidenes.

Pnictinidenes are an increasingly relevant species in main group chemistry and generally exhibit proclivity for the triplet electronic ground state. However, the elusive singlet electronic states are often desired for chemical applications. We predict the singlet-triplet energy differences (ΔEST =ESinglet -ETriplet ) of simple group 15 and 16 substituted pnictinidenes (Pn-R; Pn=P, As, Sb, or Bi) with highly reliable focal-point analyses targeting the CCSDTQ/CBS level of theory. The only cases we predict to have favorable singlet states are P-PH2 (-3.2 kcal mol-1 ) and P-NH2 (-0.2 kcal mol-1 ). ΔEST trends are discussed in light of the geometric predictions as well as qualitative natural bond order analysis to elucidate some of the important electronic structure features. Our work provides a rigorous benchmark for the ΔEST of fundamental Pn-R moieties and provides a firm foundation for the continued study of heavier pnictinidenes.

The HOX⋯SO2 (X=F, Cl, Br, I) Binary Complexes: Implications for Atmospheric Chemistry.

Sulfur dioxide and hypohalous acids (HOX, X=F, Cl, Br, I) are ubiquitous molecules in the atmosphere that are central to important processes like seasonal ozone depletion, acid rain, and cloud nucleation. We present the first theoretical examination of the HOX⋯SO2 binary complexes and the associated trends due to halogen substitution. Reliable geometries were optimized at the CCSD(T)/aug-cc-pV(T+d)Z level of theory for HOF and HOCl complexes. The HOBr and HOI complexes were optimized at the CCSD(T)/aug-cc-pV(D+d)Z level of theory with the exception of the Br and I atoms which were modeled with an aug-cc-pwCVDZ-PP pseudopotential. 27 HOX⋯SO2 complexes were characterized and the focal point method was employed to produce CCSDT(Q)/CBS interaction energies. Natural Bond Orbital analysis and Symmetry Adapted Perturbation Theory were used to classify the nature of each principle interaction. The interaction energies of all HOX⋯SO2 complexes in this study ranged from 1.35 to 3.81 kcal mol-1 . The single-interaction hydrogen bonded complexes spanned a range of 2.62 to 3.07 kcal mol-1 , while the single-interaction halogen bonded complexes were far more sensitive to halogen substitution ranging from 1.35 to 3.06 kcal mol-1 , indicating that the two types of interactions are extremely competitive for heavier halogens. Our results provide insight into the interactions between HOX and SO2 which may guide further research of related systems.

Energetics and kinetics of various cyano radical hydrogen abstractions.

The cyano radical (CN) is an abundant, open-shell molecule found in a variety of environments, including the atmosphere, the interstellar medium and combustion processes. In these environments, it often reacts with small, closed-shell molecules via hydrogen abstraction. Both carbon and nitrogen atoms of the cyano radical are reactive sites, however the carbon is more reactive with reaction barrier heights generally between 2-15 kcal mol-1 lower than those of the analogous nitrogen. The CN + HX → HCN/HNC + X, with X = H, CH3, NH2, OH, F, SiH3, PH2, SH, Cl, C2H, CN reactions have been studied at a high-level of theory, including CCSD(T)-F12a. Furthermore, kinetics were obtained over the 100-1000 K temperature range, showing excellent agreement with those rate constants that have been determined experimentally.

Kinetic Stability of Pentazole.

The utility of high energy density materials (HEDMs) comes from their thermodynamic properties which arise from specific structural features that contribute to energy storage. Studies of such structural features seek to increase our understanding of these energy storage mechanisms in order to further enhance their properties. High-nitrogen-containing HEDMs are of particular interest because they are less toxic than traditional HEDMs. Pentazole is the largest of the nitrogen rings which has been synthesized and considered for an HEDM; however, few experimental studies exist due to the difficulty involved in the synthesis, and most previous theoretical studies employed composite methods where lower level geometries were used with higher level methods. Here, the decomposition reaction of pentazole is studied. Geometries, fundamental frequencies, and energies for each of the stationary points of the decomposition pathway are computed using ab initio methods up to CCSDT(Q). Decomposition rates are calculated over a range of temperatures using canonical transition state theory in order to determine the kinetic stability of pentazole. Based on the present results, it would be difficult for pentazole to act as an HEDM, requiring temperatures close to 200 K to achieve a suitable level of stability.

Highly Strained Pn(CH)3 (Pn = N, P, As, Sb, Bi) Tetrahedranes: Theoretical Characterization.

Recent experimental research by Cummins and co-workers has established the existence of a tetrahedrane molecule with one CH moiety replaced by phosphorus. We present here the first theoretical studies of the entire Pn(CH)3 (Pn = N, P, As, Sb, Bi) class of molecules. Geometries are obtained at the highly reliable CCSD(T)/aug-cc-pwCVTZ(-PP) level of theory. Harmonic vibrational frequencies are determined and analyzed to confirm the nature of each stationary point and provide helpful findings that may aid in the detection of each species. Most notable is the result that the geometric parameters associated with the (CH)3 moiety in the tetrahedranes exhibit little change under pnictogen substitution, while the Pn-C bonds and C-Pn-C bond angles greatly increase and decrease, respectively. Strain energies are predicted and range from 122.3 kcal mol-1 (N(CH)3) to 99.4 kcal mol-1 (Bi(CH)3) at the DF-CCSD(T)//B3LYP-D3/aug-cc-pV(T+d)Z(-PP) level of theory. The obtained geometries are further analyzed with Natural Bond Orbital (NBO) methods to understand the bonding and electronic structure of each species. We also provide insight into how different substituents can help make the tetrahedrane structure more energetically favorable due to electron delocalization into substituent antibonding orbitals. The effect of additional delocalization also weakens the Pn-C bonds, especially for the heavier pnictogens. This work concludes with a list of considerations that summarize our key findings and motivate future work aimed at producing novel pnictogen-substituted tetrahedrane molecules.

Substituent Effects on Aluminyl Anions and Derived Systems: A High-Level Theory.

Aluminyl anions are low-valent aluminum species bearing a lone pair of electrons and a negative charge. These systems have drawn recent synthetic interest for their nucleophilic nature, allowing for the activation of σ-bonds, and have been proposed as a pathway to hydrogen energy storage. In this research, we provide high-level ab initio geometries and energies for both the simplest aluminyl anion (AlH2-) and several substituted derivatives. Geometries are reported using the gold-standard CCSD(T)/aug-cc-pV(T+d)Z level of theory. Energies were extrapolated to the complete basis set limit through the focal point approach, utilizing coupled-cluster methods through perturbative quadruples and basis sets up to five-ζ quality. Geometries were rationalized using electrostatic, steric, and orbital donation effects. The donation from substituents to Al is accompanied by back-donation effects, a property traditionally thought of in transition-metal systems. Stereoelectronic effects through the secondary orbital interaction play a fundamental role in stabilizing these low-valent aluminum compounds and would likely also affect the feasibility of their use within several industrial applications. The energetic analysis of the formation of each substituted anion is rationalized as the result of three energetic schemes. The effectiveness of these schemes for determining the relative formation energies is discussed.

Cumulants as the variables of density cumulant theory: A path to Hermitian triples.

We study the combination of orbital-optimized density cumulant theory and a new parameterization of reduced density matrices in which the variables are the particle-hole cumulant elements. We call this combination OλDCT. We find that this new Ansatz solves problems identified in the previous unitary coupled cluster Ansatz for density cumulant theory: the theory is now free of near-zero denominators between occupied and virtual blocks, can correctly describe the dissociation of H2, and is rigorously size-extensive. In addition, the new Ansatz has fewer terms than the previous unitary Ansatz, and the optimal orbitals delivered by the exact theory are the natural orbitals. Numerical studies on systems amenable to full configuration interaction show that the amplitudes from the previous ODC-12 method approximate the exact amplitudes predicted by this Ansatz. Studies on equilibrium properties of diatomic molecules show that even with the new Ansatz, it is necessary to include triples to improve the accuracy of the method compared to orbital-optimized linearized coupled cluster doubles. With a simple iterative triples correction, OλDCT outperforms other orbital-optimized methods truncated at comparable levels in the amplitudes, as well as coupled cluster single and doubles with perturbative triples [CCSD(T)]. By adding four more terms to the cumulant parameterization, OλDCT outperforms CCSDT while having the same O(V5O3) scaling.

Quantum Chemistry Common Driver and Databases (QCDB) and Quantum Chemistry Engine (QCEngine): Automation and interoperability among computational chemistry programs.

Community efforts in the computational molecular sciences (CMS) are evolving toward modular, open, and interoperable interfaces that work with existing community codes to provide more functionality and composability than could be achieved with a single program. The Quantum Chemistry Common Driver and Databases (QCDB) project provides such capability through an application programming interface (API) that facilitates interoperability across multiple quantum chemistry software packages. In tandem with the Molecular Sciences Software Institute and their Quantum Chemistry Archive ecosystem, the unique functionalities of several CMS programs are integrated, including CFOUR, GAMESS, NWChem, OpenMM, Psi4, Qcore, TeraChem, and Turbomole, to provide common computational functions, i.e., energy, gradient, and Hessian computations as well as molecular properties such as atomic charges and vibrational frequency analysis. Both standard users and power users benefit from adopting these APIs as they lower the language barrier of input styles and enable a standard layout of variables and data. These designs allow end-to-end interoperable programming of complex computations and provide best practices options by default.

Substituted Ortho-Benzynes: Properties of the Triple Bond.

Ortho-benzyne has been well studied by both experiment and theory. Its substituted variants, however, have been less carefully examined. Benchmark data are computed for unsubstituted ortho-benzyne using several density functional theory functionals and basis sets, up to cc-pVQZ. Optimized geometries for the substituted ortho-benzyne as well as harmonic vibrational frequencies and singlet-triplet splittings are computed using the benchmarked functionals. A proximal (syn)OH substitution causes a mean θ1 distortion of +8.1 ± 1.4° from ortho-benzyne. Substituting in the proximal position with F shifts the singlet-triplet splitting by +4.5 ± 0.4 kcal mol-1 from ortho-benzyne. Natural bond orbital analysis, including natural Coulomb electrostatics, elucidates the presence of three influences from the selected substituents: hyperconjugative, resonance, and electrostatic effects.

High level ab initio investigation of the catalytic effect of water on formic acid decomposition and isomerization.

Formic acid (FA) is a ubiquitous molecule found in the atmosphere, and is relevant to many important processes. The FA molecule generally exists as the trans isomer, which can decompose into H2O and CO (dehydration). It can also exist in the less favorable cis isomer which can decompose into H2 and CO2 (decarboxylation). Our work examines the complexes formed between each isomer of FA with water. We present geometries and vibrational frequencies obtained at the reliable CCSD(T)/aug-cc-pVTZ level of theory for seven FAwater complexes. We utilize the focal point method to determine CCSDT(Q)/CBS plus corrections binding energies of 7.37, 3.36, and 2.02 kcal mol-1 plus 6.07, 3.79, 2.60, and 2.55 kcal mol-1 for the trans-FAwater and cis-FAwater complexes, respectively. Natural bond orbital analysis is used to further decompose the interactions in each complex and gain insight into their relative strengths. Furthermore, we examine the effect that a single water molecule has on the barrier heights to each decomposition pathway by optimizing the transition states and verifying their connectivity with intrinsic reaction coordinate computations as well as utilizing a kinetic model. Water lowers the barrier to dehydration by at most 15.78 kcal mol-1 and the barrier to decarboxylation by up to 15.90 kcal mol-1. Our research also examines for the first time the effect of one water molecule on the interconversion barrier and we find that the barrier from trans to cis is not catalyzed by water due to the strong FA and water interactions. Our results highlight some instances where different binary complexes result in different decomposition pathways and even a case where one binary complex can form the same decomposition products via two distinct mechanisms. Our results provide a reliable benchmark of the FAH2O system as well as provide insight into future studies of similar atmospheric systems.

The atmospheric importance of methylamine additions to Criegee intermediates.

Criegee intermediates are important targets for study in atmospheric chemistry because of their capacity to oxidize airborne species. Among these species, ammonia has received critical attention for its presence in polluted agricultural or industrial areas and its role in forming particulate matter and condensation nuclei. Although methylamine has been given less attention than ammonia, both theoretical and experimental studies have demonstrated that the additional methyl substitution on the ammonia derivatives increases the rate constants for some systems. This suggests that the methylamine addition to Criegee intermediates could be more significant to atmospheric processes. In this work, geometries are optimized at the DF-CCSD(T)/ANO1 level for the methylamine addition reactions to the simplest Criegee intermediate and the anti- and syn-methylated Criegee intermediates. Energies for each stationary point were computed at the CCSD(T)/CBS level with corrections from the CCSDT(Q) method. Rate constants are obtained for each reaction using canonical transition state theory. Although methylamine addition proved to be a more favorable reaction relative to ammonia addition, the significantly lower concentration of atmospheric methylamine limits the prevalence of these reactions, even in the most optimal conditions. It is unlikely that the methylamine addition to Criegee intermediates will contribute significantly to the consumption of Criegee intermediates in the atmosphere.