Correction: Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance.

Correction for 'Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance' by Pascal Vermeeren et al., Phys. Chem. Chem. Phys., 2022, 24, 18028-18042, https://doi.org/10.1039/D2CP02234F.

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.

Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance.

Hierarchical, convergent ab initio benchmark computations were performed followed by a systematic analysis of DFT performance for five pericyclic reactions comprising Diels-Alder, 1,3-dipolar cycloaddition, electrocyclic rearrangement, sigmatropic rearrangement, and double group transfer prototypes. Focal point analyses (FPA) extrapolating to the ab initio limit were executed via explicit quantum chemical computations with electron correlation treatments through CCSDT(Q) and correlation-consistent Gaussian basis sets up to aug'-cc-pV5Z. Optimized geometric structures and vibrational frequencies of all stationary points were obtained at the CCSD(T)/cc-pVTZ level of theory. The FPA reaction barriers and energies exhibit convergence to within a few tenths of a kcal mol-1. The FPA benchmarks were used to evaluate the performance of 60 density functionals (eight dispersion-corrected), covering the local-density approximation (LDA), generalized gradient approximations (GGAs), meta-GGAs, hybrids, meta-hybrids, double-hybrids, and range-separated hybrids. The meta-hybrid M06-2X functional provided the best overall performance [mean absolute error (MAE) of 1.1 kcal mol-1] followed closely by the double-hybrids B2K-PLYP, mPW2K-PLYP, and revDSD-PBEP86 [MAE of 1.4-1.5 kcal mol-1]. The regularly used GGA functional BP86 gave a higher MAE of 5.8 kcal mol-1, but it qualitatively described the trends in reaction barriers and energies. Importantly, we established that accurate yet efficient meta-hybrid or double-hybrid DFT potential energy surfaces can be acquired based on geometries from the computationally efficient and robust BP86/DZP level.

Catalyzed reaction of isocyanates (RNCO) with water.

The reactions between substituted isocyanates (RNCO) and other small molecules (e.g. water, alcohols, and amines) are of significant industrial importance, particularly for the development of novel polyurethanes and other useful polymers. We present very high-level ab initio computations on the HNCO + H2O reaction, with results targeting the CCSDT(Q)/CBS//CCSD(T)/cc-pVQZ level of theory. Our results affirm that hydrolysis can occur across both the N[double bond, length as m-dash]C and C[double bond, length as m-dash]O bonds of HNCO via concerted mechanisms to form carbamate or imidic acid with ΔH0K barrier heights of 38.5 and 47.5 kcal mol-1. A total of 24 substituted RNCO + H2O reactions were studied. Geometries obtained with a composite method and refined with CCSD(T)/CBS single point energies determine that substituted RNCO species have a significant influence on these barrier heights, with an extreme case like fluorine lowering both barriers by close to 15 kcal mol-1 and most common alkyl substituents lowering both by approximately 3 kcal mol-1. Natural Bond Orbital (NBO) analysis provides evidence that the predicted barrier heights are strongly associated with the occupation of the in-plane C-O* orbital of the RNCO reactant. Key autocatalytic mechanisms are considered in the presence of excess water and RNCO species. Additional waters (one or two) are predicted to lower both barriers significantly at the CCSD(T)/aug-cc-pV(T+d)Z level of theory with strongly electron withdrawing RNCO substituents also increasing these effects, similar to the uncatalyzed case. The 298 K Gibbs energies are only marginally lowered by a second catalyst water molecule, indicating that the decreasing ΔH0K barriers are offset by loss of translational entropy with more than one catalyst water. Two-step 2RNCO + H2O mechanisms are characterized for the formation of carbamate and imidic acid. The second step of these two pathways exhibits the largest barrier and presents no clear pattern with respect to substituent choice. Our results indicate that an additional RNCO molecule might catalyze imidic acid formation but have less influence on the efficiency of carbamate formation. We expect that these results lay a firm foundation for the experimental study of substituted isocyanates and their relationship to the energetic pathways of related systems.

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.

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.

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.

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.

Important features of the potential energy surface of the methylamine plus O(1D) reaction.

This research presents an ab initio characterization of the potential energy surface for the methylamine plus 1D oxygen atom reaction, which may be relevant to interstellar chemistry. Geometries and harmonic vibrational frequencies were determined for all stationary points at the CCSD(T)/aug-cc-pVTZ level of theory. The focal point method along with several additive corrections was used to obtain reliable CCSDT(Q)/CBS potential energy surface features. Extensive conformational analysis and intrinsic reaction coordinate computations were performed to ensure accurate chemical connectivity of the stationary points. Five minima were determined to be possible products of this reaction and three novel transition states were found that were previously unreported or mislabeled in the literature. The pathways we present can be used to guide further searches for NH2 containing species in the interstellar medium.

A comparison between hydrogen and halogen bonding: the hypohalous acid-water dimers, HOXH2O (X = F, Cl, Br).

Hypohalous acids (HOX) are a class of molecules that play a key role in the atmospheric seasonal depletion of ozone and have the ability to form both hydrogen and halogen bonds. The interactions between the HOX monomers (X = F, Cl, Br) and water have been studied at the CCSD(T)/aug-cc-pVTZ level of theory with the spin free X2C-1e method to account for scalar relativistic effects. Focal point analysis was used to determine CCSDT(Q)/CBS dissociation energies. The anti hydrogen bonded dimers were found with interaction energies of -5.62 kcal mol-1, -5.56 kcal mol-1, and -4.97 kcal mol-1 for X = F, Cl, and Br, respectively. The weaker halogen bonded dimers were found to have interaction energies of -1.71 kcal mol-1 and -3.03 kcal mol-1 for X = Cl and Br, respectively. Natural bond orbital analysis and symmetry adapted perturbation theory were used to discern the nature of the halogen and hydrogen bonds and trends due to halogen substitution. The halogen bonds were determined to be weaker than the analogous hydrogen bonds in all cases but close enough in energy to be relevant, significantly more so with increasing halogen size.