Search

The structures and energetics of the binuclear cyclopentadienylmetal alkyne systems Cp 2 M 2 C 2 R 2 (M = Ni, Co, Fe; R = Me and NMe 2 ) have been investigated using density functional theory. For the Cp 2 M 2 C 2 (NMe 2 ) 2 (M = Ni, Co, Fe) systems the relative energies of isomeric tetrahedrane Cp 2 M 2 (alkyne) structures having intact alkyne ligands and alkyne dichotomy structures Cp 2 M 2 (CNMe 2 ) 2 in which the C[triple bond, length as m-dash]C triple bond of the alkyne has broken completely to give separate Me 2 NC units depending on the central metal atoms. For the nickel system Cp 2 Ni 2 C 2 (NMe 2 ) 2 as well as the related nickel systems Cp 2 Ni 2 (MeC 2 NMe 2 ) and Cp 2 Ni 2 C 2 Me 2 the tetrahedrane structures are clearly preferred energetically consistent with the experimental syntheses of several stable Cp 2 Ni 2 (alkyne) complexes. The tetrahedrane and alkyne dichotomy structures have similar energies for the Cp 2 Co 2 C 2 (NMe 2 ) 2 system whereas the alkyne dichotomy structures are significantly energetically preferred for the Cp 2 Fe 2 C 2 (NMe 2 ) 2 system. The potential energy surfaces for the Cp 2 M 2 (MeC 2 NMe 2 ) and Cp 2 M 2 C 2 Me 2 systems (M = Co, Fe) are complicated by low-energy structures in which hydrogen migration occurs from the alkyne methyl groups to one or both alkyne carbon atoms to give Cp 2 M 2 (C 3 H 3 NMe 2 ) and Cp 2 M 2 (C 3 H 3 Me) derivatives with bridging metalallylic ligands, Cp 2 M 2 (CH 2 [double bond, length as m-dash]C[double bond, length as m-dash]CHNMe 2 ) and Cp 2 M 2 (CH 2 [double bond, length as m-dash]C[double bond, length as m-dash]CHMe) with bridging allene ligands, as well as Cp 2 M 2 (CH 2 [double bond, length as m-dash]CH-CNMe 2 ) and Cp 2 M 2 (CH 2 [double bond, length as m-dash]CH-CHMe) with bridging vinylcarbene ligands. For the Cp 2 M 2 C 2 Me 2 (M = Co, Fe) systems migration of a hydrogen atom from each methyl group to an alkyne carbon atom can give relatively low-energy Cp 2 M 2 (CH 2 [double bond, length as m-dash]CH-CH[double bond, length as m-dash]CH 2 ) structures with a bridging butadiene ligand. Five transition states have been identified in a proposed mechanism for the conversion of the Cp 2 Co 2 /MeC[double bond, length as m-dash]CNMe 2 system to the cobaltallylic complex Cp 2 Co 2 (C 3 H 3 NMe 2 ) with intermediates having agostic C-H-Co interactions and an activation energy barrier sequence of 13.1, 17.0, 15.2, and 12.0 kcal mol -1 ., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

We present an efficient, asymptotically linear-scaling implementation of the canonically O ( N 8 ) coupled-cluster method with singles, doubles, and full triples excitations (CCSDT) method. We apply the domain-based local pair natural orbital (DLPNO) approach for computing CCSDT amplitudes. Our method, called DLPNO-CCSDT, uses the converged coupled-cluster amplitudes from a preceding DLPNO-CCSD(T) computation as a starting point for the solution of the CCSDT equations in the local natural orbital basis. To simplify the working equations, we t 1 -dress our two-electron integrals and Fock matrices, allowing our equations to take on the form of CCDT. With appropriate parameters, our method can recover more than 99.99% of the total canonical CCSDT correlation energy. In addition, we demonstrate that our method consistently yields sub-kJ mol -1 errors in relative energies when compared to canonical CCSDT, and, likewise, when computing the difference between CCSDT and CCSD(T). Finally, to highlight the low scaling of our algorithm, we present timings on linear alkanes (up to 30 carbons and 730 basis functions) and water clusters (up to 131 water molecules and 3144 basis functions).

The isolation of nucleophilic boron bases has led to a paradigm shift in boron chemistry. Previous studies of the bis(carbene) borylene complexes revealed that these compounds possess strong donor abilities, and their reaction inertness is due to the large steric hindrance between boron reagents and reactant. In the present study, we have theoretically studied the [(N 5 ) 2 BX] 2- and [(N 5 ) 2 B 2 X 2 ] 2- compounds (X = H, F, Cl, Br). Their electronic structures and properties are discussed by using the NBO, LOL, and ELF methods. We found that both π-conjugation and hyperconjugation effects can effectively stabilize the substituted nucleophilic anionic boron compounds [(N 5 ) 2 BX] 2- and [(N 5 ) 2 B 2 X 2 ] 2- . Substituents, especially X = H, stabilize the boron center through highly delocalized π-bonding, involving the formally "empty" in-plane p orbitals of the boron atom. While the halogen substituents have high electron withdrawal ability, leading to systems being less stable, we suggest the borinium anions [(N 5 ) 2 BH] 2- and [(N 5 ) 2 B 2 H 2 ] 2- as possible synthetic targets of novel environmentally friendly catalysts.

Vacuum-ultraviolet (VUV) absorption spectroscopy enables electronic transitions that offer the unambiguous identification of molecules. As target molecules become more complex, multifunctional species present a great challenge to both experimental and computational spectroscopy. This research reports both experimental and theoretical studies of oxiranes. Computationally, the nuclear ensemble approach has been used to accurately predict experimental spectra for a variety of molecules. However, this approach incurs great computational cost, as ensembles generally consist of thousands of geometries. The present study aims to drastically reduce the ensemble by evaluating the significance of the conformers to the predicted spectra. This approach was applied to 11 substituted oxiranes using the Conformer Rotamer Ensemble Sampling Tool (CREST) of Grimme to generate an ensemble of unique conformers determined by their Boltzmann populations. Five TD-DFT functionals (BMK, CAM-B3LYP, M06-2X, MN15, ωB97X-D) and EOM-CCSD were used to simulate the spectrum of each substituted oxirane ensemble. Computed spectra were then compared to the experiment using both qualitative and quantitative metrics. Based on these metrics, it was observed that certain conformers may not be necessary to characterize this set of oxiranes despite the temperature (323 K) of the experiment. A single conformer can then be used with TD-DFT and EOM-CCSD to replicate the experimental spectra of these medium-sized combustion species.

Ring size effects on geometries and electronic structures were investigated for the (C n H n )M(C m H m ) ( n = 4, 5, or 6; m = 8, 7, or 6; m + n = 12; M = Ti-Ni) systems using density functional theory. The lowest-energy C 12 H 12 M structures for the early transition metals titanium, vanadium, and chromium are the experimentally known singlet (η 5 -C 5 H 5 )Ti(η 7 -C 7 H 7 ), doublet (η 5 -C 5 H 5 )V(η 7 -C 7 H 7 ), and singlet (η 6 -C 6 H 6 ) 2 Cr, respectively. The likewise experimentally known singlet (η 6 -C 6 H 6 ) 2 Ti, doublet (η 6 -C 6 H 6 ) 2 V, and singlet (η 5 -C 5 H 5 )Cr(η 7 -C 7 H 7 ) are the second-lowest-energy structures with only a small energy difference between the two vanadium structures. For the later transition metals, dibenzenemetal complexes are the lowest-energy C 12 H 12 M species with two fully bonded hexahapto benzene rings in the lowest-energy manganese and iron derivatives and one hexahapto and one dihapto benzene ring in the lowest-energy cobalt and nickel derivatives. The lowest-energy (C 5 H 5 )M(C 7 H 7 ) structures for the later transition metals iron, cobalt, and nickel have partially bonded nonplanar C 7 H 7 rings with one or two uncomplexed C=C bonds. The (C 4 H 4 )M(C 8 H 8 ) (M = Ti-Ni) structures with the metal sandwiched between four- and eight-membered rings were found to be much higher in energy than their (C 5 H 5 )M(C 7 H 7 ) and (C 6 H 6 ) 2 M isomers., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The permeability glycoprotein, encoded by the ABCB1 gene, is widely implicated in multidrug resistance (MDR), as it has been shown to reduce the intracellular concentration of most small molecule therapeutics, including the majority of the breakpoint cluster region Abelson proto-oncogene 1 (BCR-ABL1) kinase inhibitors used in the treatment of Philadelphia chromosome positive (Ph+) leukemias. With this in mind, we describe an integrated theoretical and experimental approach to shed light on substituent effects in the pendant anilino moiety of 4-anilinoquinazolines and 4-anilinoquinoline-3-carbonitrile-based kinase inhibitors and their influence on P-gp-mediated efflux. This analysis culminated in the identification of a hydroxylamine-bearing, dual cSRC/BCR-ABL1 kinase inhibitor 16a that exhibits a marked reduction in P-gp-mediated efflux ratio and potent activity in a Ph+ patient-derived cell line (K562) and an MDR-Ph+ patient-derived cell line (K562/Dox) overexpressing P-gp. Overall, we demonstrate that the P-gp-mediated efflux ratio can be minimized by computationally driven optimization of the molecular dipole and/or cp K a without recourse to intramolecular hydrogen bonds.

Automatic differentiation (AD) offers a route to achieve arbitrary-order derivatives of challenging wave function methods without the use of analytic gradients or response theory. Currently, AD has been predominantly used in methods where first- and/or second-order derivatives are available, but it has not been applied to methods lacking available derivatives. The most robust approximation of explicitly correlated MP2, MP2-F12/3C(FIX)+CABS, is one such method. By comparing the results of MP2-F12 computed with AD versus finite-differences, it is shown that (a) optimized geometries match to about 10 -3 Å for bond lengths and a 10 -6 degree for angles, and (b) dipole moments match to about 10 -6 D. Hessians were observed to have poorer agreement with numerical results (10 -5 ), which is attributed to deficiencies in AD implementations currently. However, it is notable that vibrational frequencies match within 10 -2 cm -1 . The use of AD also allowed the prediction of MP2-F12/3C(FIX)+CABS IR intensities for the first time.

Fulminic acid (HCNO) played a critical role in the early development of organic chemistry, and chemists have sought to discern the structure and characteristics of this molecule and its isomers for over 200 years. The mercurial nature of the extremely flat H-C-N bending potential of fulminic acid, with a nearly vanishing harmonic vibrational frequency at linearity, remains enigmatic and refractory to electronic structure theory, as dramatic variation with both orbital basis set and electron correlation method is witnessed. To solve this problem using rigorous electronic wavefunction methods, we have employed focal point analyses (FPA) to ascertain the ab initio limit of optimized linear and bent geometries, corresponding vibrational frequencies, and the HCN + O( 3 P ) → HCNO reaction energy. Electron correlation treatments as extensive as CCSDT(Q), CCSDTQ(P), and even CCSDTQP(H) were employed, and complete basis set (CBS) extrapolations were performed using the cc-pCV X Z ( X = 4-6) basis sets. Core electron correlation, scalar relativistic effects (MVD1), and diagonal Born-Oppenheimer corrections (DBOC) were all included and found to contribute significantly in determining whether vibrationless HCNO is linear or bent. At the all-electron (AE) CCSD(T)/CBS level, HCNO is a linear molecule with ω 5 (H-C-N bend) = 120 cm -1 . However, composite AE-CCSDT(Q)/CBS computations give an imaginary frequency (51 i cm -1 ) at the linear optimized geometry, leading to an equilibrium structure with an H-C-N angle of 173.9°. Finally, at the AE-CCSDTQ(P)/CBS level, HCNO is once again linear with ω 5 = 45 cm -1 , and inclusion of both MVD1 and DBOC effects yields ω 5 = 32 cm -1 . A host of other topics has also been investigated for fulminic acid, including the dependence of r e and ω i predictions on a variety of CBS extrapolation formulas, the question of multireference character, the N-O bond energy and enthalpy of formation, and issues that give rise to the quasibent appellation.

Context: 2,2,2-Trifluoroethanol (TFE) is known as a membrane mimetic solvent. The IR spectrum, 1 H NMR spectrum, 13 C NMR spin‒lattice relaxation times (T 1 ), and nuclear Overhauser effect (NOE) data are consistent with extensive hydrogen bonding in TFE, but do not lead to structural features of the hydrogen bonding. Hence, DFT computations were carried out. The results predict the existence of a set of H-bonded dimers and trimers. The bond lengths and dihedral angles in these complexes are obtained, together with their dissociation energies. Computations were also performed for the geometry of the two conformers of the isolated monomer. The structure of one of the dimers consists of a 7-member cyclic fragment with a free CF 3 CH 2 side chain. One set of the trimer structures involves the OH of a third monomer H-bonding to one of the F atoms in the CF 3 group of the side chain of this dimer, thereby creating three trimer isomers. A fourth trimer cluster is formed from three monomers in which three OH∙∙∙O bonds create a cyclic fragment with three CF 3 CH 2 side chains. The high dissociation energy (with respect to three monomers) indicates the high stability of the trimer complexes. The structural features of the trimer complexes resemble the structure of a conventional liquid crystal molecule and are postulated to resemble the latter in properties and function in solution, but at a much shorter timescale because of the noncovalent bonding. This hydrogen bonding phenomenon of TFE may be related to its function as a membrane memetic solvent., Methods: Initially, IR and NMR spectroscopic methods were used. Standard procedures were followed. For the computations, a hybrid DFT method with empirical dispersion, ωB97X-D, was used. The basis set, 6-311++G**, is of triple-ζ quality, in which polarization functions and diffuse functions were added for all atoms., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Group 14 M 2 H 2 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 Sn 2 H 2 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 Sn 2 H 2 . Our results provide insights into the important Sn-H interaction and provide guidance for future work that may detect S n 2 H 2 + in the laboratory for the first time.

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)., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

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., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The ethynyl radical, C 2 H, is found in a variety of different environments ranging from interstellar space and planetary atmospheres to playing an important role in the combustion of various alkynes under fuel-rich conditions. Hydrogen-atom abstraction reactions are common for the ethynyl radical in these contrasting environments. In this study, the C 2 H + HX → C 2 H 2 + X, where HX = HNCO, trans -HONO, cis -HONO, C 2 H 4 , and CH 3 OH, reactions have been investigated at rigorously high levels of theory, including CCSD(T)-F12a/cc-pVTZ-F12. For the stationary points thus located, much higher levels of theory have been used, with basis sets as large as aug-cc-pV5Z and methods up to CCSDT(Q), and core correlation was also included. These molecules were chosen because they can be found in either interstellar or combustion environments. Various additive energy corrections have been included to converge the relative enthalpies of the stationary points to subchemical accuracy (≤0.5 kcal mol -1 ). Barriers predicted here (2.19 kcal mol -1 for the HNCO reaction and 0.47 kcal mol -1 for C 2 H 4 ) are significantly lower than previous predictions. Reliable kinetics were acquired over a wide range of temperatures (50-5000 K), which may be useful for future experimental studies of these reactions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

A stable aluminum tris(dithiolene) triradical ( 3 ) was experimentally realized through a low-temperature reaction of the sterically demanding lithium dithiolene radical ( 2 ) with aluminum iodide. Compound 3 was characterized by single-crystal X-ray diffraction, UV-vis and EPR spectroscopy, SQUID magnetometry, and theoretical computations. The quartet ground state of triradical 3 has been unambiguously confirmed by variable-temperature continuous wave EPR experiments and SQUID magnetometry. Both SQUID magnetometry and broken-symmetry DFT computations reveal a small doublet-quartet energy gap [Δ E DQ = 0.18 kcal mol -1 (SQUID); Δ E DQ = 0.14 kcal mol -1 (DFT)]. The pulsed EPR experiment (electron spin echo envelop modulation) provides further evidence for the interaction of these dithiolene-based radicals with the central aluminum nucleus of 3 .

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., (© 2024 Wiley Periodicals LLC.)

Five structures of Ge 2 H 2 and Ge 2 H 2 + 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 Ge 2 H 2 + structures is butterfly, germylidene, monobridged, trans , then linear. In neutral Ge 2 H 2 , 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 Ge 2 H 2 + is contained in the region of the Ge-Ge bond.

While the dithiolene-based N-heterocyclic silane (4) reacts with two equivalents of BX 3 (X = Br, I) to give zwitterionic Lewis adducts 5 and 8, respectively, the parallel reaction of 4 with BCl 3 results in 10, a dithiolene-substituted N-heterocyclic silane, via the Si-S bond cleavage. Unlike 5, the labile 8 may be readily converted to 9 via BI 3 -mediated cleavage of the Si-N bond. The formation of 5 and 8 confirms that 4 uniquely possesses dual nucleophilic sites: (a) the terminal sulphur atom of the dithiolene moiety; and (b) the backbone carbon of the N-heterocyclic silane unit.

High-level potential energy surfaces for three reactions of hypobromous acid with atomic hydrogen were computed at the CCSDTQ/CBS//CCSDT(Q)/complete basis set level of theory. Focal point analysis was utilized to extrapolate energies and gradients for energetics and optimizations, respectively. The H attack at Br and subsequent Br-O cleavage were found to proceed barrierlessly. The slightly submerged transition state lies -0.2 kcal mol-1 lower in energy than the reactants and produces OH and HBr. The two other studied reaction paths are the radical substitution to produce H2O and Br with a 4.0 kcal mol-1 barrier and the abstraction at hydrogen to produce BrO and H2 with an 11.2 kcal mol-1 barrier. The final product energies lie -37.2, -67.9, and -7.3 kcal mol-1 lower in energy than reactants, HOBr + H, for the sets of products OH + HBr, H2O + Br, and H2 + BrO, respectively. Additive corrections computed for the final energetics, particularly the zero-point vibrational energies and spin-orbit corrections, significantly impacted the final stationary point energies, with corrections up to 6.2 kcal mol-1., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The industrial production of methanol through CO hydrogenation using the Cu/ZnO/Al 2 O 3 catalyst requires harsh conditions, and the development of new catalysts with low operating temperatures is highly desirable. In this study, organic biomimetic FLP catalysts with good tolerance to CO poison are theoretically designed. The base-free catalytic reaction contains the 1,1-addition of CO into a formic acid intermediate and the hydrogenation of the formic acid intermediate into methanol. Low-energy spans (25.6, 22.1, and 20.6 kcal/mol) are achieved, indicating that CO can be hydrogenated into methanol at low temperatures. The new extended aromatization - dearomatization effect involving multiple rings is proposed to effectively facilitate the rate-determining CO 1,1-addition step, and a new CO activation model is proposed for organic catalysts., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

E 2 H 2 (E = As, Sb, Bi) structures involving multiple bonds have attracted much attention recently. The E 2 H 3 + cations (protonated E 2 H 2 ) are predicted to be viable with substantial proton affinities (>180 kcal/mol). Herein, the bonding characters and energetics of a number of E 2 H 3 + isomers are explored through CCSD(T) and DFT methods. For the As 2 H 3 + system, the CCSD(T)/cc-pVQZ-PP method predicts that the vinylidene-like structure lies lowest in energy, with the trans and cis isomers higher by 6.7 and 9.3 kcal/mol, respectively. However, for Sb 2 H 3 + and Bi 2 H 3 + systems, the trans isomer is the global minimum, while the energies of the cis and vinylidene-like structures are higher, respectively, by 2.0 and 2.4 kcal/mol for Sb 2 H 3 + and 1.6 and 15.0 kcal/mol for Bi 2 H 3 + . Thus, the vinyledene-like structure is the lowest energy for the arsenic system but only a transition state of the bismuth system. With permanent dipole moments, all minima may be observable in microwave experiments. Besides, we have also obtained transition states and planar-cis structures with higher energies. The current results should provide new insights into the various isomers and provide a number of predictions for future experiments.

The 1 : 2 reaction of the imidazole-based dithiolate (2) with GeCl 2  • dioxane in THF/TMEDA gives 3, a TMEDA-complexed dithiolene-based germylene. Compound 3 is converted to monothiolate-complexed (5) and N-heterocyclic carbene-complexed (7) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis-dithiolene-based germylene (8), involving a 3c-4e S-Ge-S bond, has also been synthesized through controlled hydrolysis of 7. The bonding nature of 3, 5, and 8 was investigated by both experimental and theoretical methods., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

This study systematically examines the interactions of the tetrafluoroborate anion (BF 4 - ) with up to four water molecules (BF 4 - (H 2 O) n =1,2,3,4 ). Full geometry optimizations and subsequent harmonic vibrational frequency computations are performed using a variety of density functional theory (DFT) methods (B3LYP, B3LYP-D3BJ, and M06-2X) and the MP2 ab initio method with a triple-ζ correlation consistent basis set augmented with diffuse functions on all non-hydrogen atoms (cc-pVTZ for H and aug-cc-pVTZ for B, O, and F; denoted as haTZ). Optimized structures and harmonic vibrational frequencies were also obtained with the CCSD(T) ab initio method and the haTZ basis set for the mono- and dihydrate ( n = 1, 2) structures. The 2-body:Many-body (2b:Mb) technique, in which CCSD(T) computations capture the 1- and 2-body contributions to the interactions and MP2 computations recover all higher-order contributions, was used to extend these demanding computations to the tri- and tetrahydrate ( n = 3, 4) systems. Four, five, and eight new stationary points have been identified for the di-, tri-, and tetrahydrate systems, respectively. The global minimum of the monohydrate adopts a symmetric double ionic hydrogen bond motif with C 2 v symmetry and an electronic dissociation energy of 13.17 kcal mol -1 at the CCSD(T)/haTZ level of theory. This strong solvent···solute interaction, however, competes with solute···solute interactions in the lowest-energy BF 4 - (H 2 O) n =2,3,4 minima that are not seen in the other di-, tri-, or tetrahydrate minima. The latter interactions help increase the 2b:Mb dissociation energies to more than 26, 41, and 51 kcal mol -1 for n = 2, 3, and 4, respectively. Structures that form hydrogen bonds between the solvating water molecules also exhibit the largest shifts in the harmonic OH stretching frequencies for the waters of hydration. These shifts can exceed -280 cm -1 relative to an isolated H 2 O molecule at the 2b:Mb/haTZ level of theory.

The 1:1 reaction of the carbene-stabilized dithiolene zwitterion 1 with BH 3 ·SMe 2 gave the dithiolene-based hydroborane 2 and the doubly hydrogen-capped CAAC species 3 via hydride-coupled reverse electron transfer processes. The mechanism of this transformation was probed computationally using density functional theory. The subsequent 2:1 reaction of 2 with 1 resulted in 4 and 3 , suggesting that 1 can mediate the B-H bond activation not only for BH 3 but also for monohydroboranes. In the presence of BH 3 ·SMe 2 , 2 was unexpectedly converted to the corresponding diborane(4) complex 5 through a dehydrocoupling reaction at an elevated temperature., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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.

We present the working equations for a reduced-scaling method of evaluating the perturbative triples (T) energy in coupled-cluster theory, through the tensor hypercontraction (THC) of the triples amplitudes ( t ijk abc ). Through our method, we can reduce the scaling of the (T) energy from the traditional O ( N 7 ) to a more modest O ( N 5 ) . We also discuss implementation details to aid future research, development, and software realization of this method. Additionally, we show that this method yields submillihartree (mEh) differences from CCSD(T) when evaluating absolute energies and sub-0.1 kcal/mol energy differences when evaluating relative energies. Finally, we demonstrate that this method converges to the true CCSD(T) energy through the systematic increasing of the rank or eigenvalue tolerance of the orthogonal projector, as well as exhibiting sublinear to linear error growth with respect to system size.

The synthesis of novel aluminyl anion complexes has been well exploited in recent years. Moreover, the elucidation of the structure and reactivity of these complexes opens the path toward a new understanding of low-valent aluminum complexes and their chemistry. This work computationally treats the substituent effect on aluminyl anions to discover suitable alternatives for H 2 activation at a high level of theory utilizing coupled-cluster techniques extrapolated to the complete basis set. The results reveal that the simplest AlH 2 - system is the most reactive toward the activation of H 2 , but due to the low steric demand, severe difficulty in the stabilization of this system makes its use nonviable. However, the results indicate that, in principle, aluminyl systems with -C, -CN, -NC, and -N chelating centers would be the best choices of ligand toward the activation of molecular hydrogen by taking care of suitable steric demand to prevent dimerization of the catalysts. Furthermore, computations show that monosubstitution (besides -H) in aluminyl anions is preferred over disubstitution. So our predictions show that bidentate ligands may yield less reactive aluminyl anions to activate H 2 than monodentate ones.

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.

Three different pathways for the atomic iodine plus water trimer reaction I + (H 2 O) 3 → HI + (H 2 O) 2 OH were preliminarily examined by the DFT-MPW1K method. Related to previous predictions for the F/Cl/Br + (H 2 O) 3 reactions, three pathways for the I + (H 2 O) 3 reaction are linked in terms of geometry and energetics. To legitimize the results, the "gold standard" CCSD(T) method was employed to investigate the lowest-lying pathway with the correlation-consistent polarized valence basis set up to cc-pVQZ(-PP). According to the CCSD(T)/cc-pVQZ(-PP)//CCSD(T)/cc-pVTZ(-PP) results, the I + (H 2 O) 3 → HI + (H 2 O) 2 OH reaction is predicted to be endothermic by 47.0 kcal mol -1 . The submerged transition state is predicted to lie 43.7 kcal mol -1 above the separated reactants. The I···(H 2 O) 3 entrance complex lies below the separated reactants by 4.1 kcal mol -1 , and spin-orbit coupling has a significant impact on this dissociation energy. The HI···(H 2 O) 2 OH exit complex is bound by 4.3 kcal mol -1 in relation to the separated products. Compared with simpler I + (H 2 O) 2 and I + H 2 O reactions, the I + (H 2 O) 3 reaction is energetically between them in general. It is speculated that the reaction between the iodine atom and the larger water clusters may be energetically analogous to the I + (H 2 O) 3 reaction. The iodine reaction I + (H 2 O) 3 is connected with the analogous valence isoelectronic bromine/chlorine reactions Br/Cl + (H 2 O) 3 but much different from the F + (H 2 O) 3 reaction. Significant difference with other halogen systems, especially for barrier heights, are seen for the iodine systems.

The Concordant Mode Approach (CMA) is advanced as a novel hierarchy for increasing the system size and level of theory feasible for quantum chemical computations of harmonic vibrational frequencies. The key concept behind CMA is that transferrable, internal-coordinate normal modes computed at an appropriate lower level of theory (B) comprise a superb basis for converging to vibrational frequencies given by a higher level of theory (A). Accordingly, high-level harmonic frequencies can be evaluated via CMA from a collection of single-point energies that essentially scales linearly in the number of atoms, providing nearly order-of-magnitude CPU time speedups. The accuracy of CMA methods was established by comprehensive tests on over 120 molecules for target Level A = CCSD(T)/cc-pVTZ with auxiliary Level B choices of both CCSD(T)/cc-pVDZ and B3LYP/6-31G(2 df,p ). Remarkably, the frequency residuals given by the diagonal CMA-0A(nc) scheme exhibit mean absolute deviations (MADs) of only 0.2 cm -1 and standard deviations less than 0.5 cm -1 ; the corresponding zero-point vibrational energies (ZPVEs) have negligible errors in the vicinity of 0.3 cm -1 .

Heavy aldehyde and ketone analogues, R 2 X═O (X = Si, Ge, Sn, or Pb), differ from their R 2 C═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, H 2 Sn═O and H 2 Pb═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 H 2 X═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 H 2 X═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 H 2 Sn═O or H 2 Pb═O for the first time.

A carbene-stabilized dithiolene zwitterion ( 3 ) activates ammonia, affording 4 • and 5 , through both single-electron transfer (SET) and hydrogen atom transfer (HAT). Reaction products were characterized spectroscopically and by single-crystal X-ray diffraction. The mechanism of the formation of 4 • and 5 was probed by experimental and computational methods. This discovery is the first example of metal-free ammonia activation via HAT.

Butyl radicals (n-, s-, i-, and tert-butyl) are formed from the pyrolysis of stable precursors (1-pentyl nitrite, 2-methyl-1-butyl nitrite, isopentyl nitrite, and azo-tert-butane, respectively). The radicals are doped into a beam of liquid helium droplets and probed with infrared action spectroscopy from 2700 to 3125 cm -1 , allowing for a low temperature measurement of the CH stretching region. The presence of anharmonic resonance polyads in the 2800-3000 cm -1 region complicates its interpretation. To facilitate spectral assignment, the anharmonic resonances are modeled with two model Hamiltonian approaches that explicitly couple CH stretch fundamentals to HCH bend overtones and combinations: a VPT2+K normal mode model based on coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] quartic force fields and a semi-empirical local mode model. Both of these computational methods provide generally good agreement with the experimental spectra.

Chemical bond territory is rich with covalently bonded molecules wherein a strong bond is formed by equal or unequal sharing of a quantum of electrons. The noncovalent version of the bonding scenarios expands the chemical bonding territory to a weak domain wherein the interplay of electrostatic and π-effects, dipole-dipole, dipole-induced dipole, and induced dipole-induced dipole interactions, and hydrophobic effects occur. Here we study both the covalent and noncovalent interactive behavior of cyclic and acyclic imine-based functional molecules (XN) with CO 2 . All parent XN systems preferred the formation of noncovalent ( nc ) complex XN···CO 2 , while more saturated such systems (XN') produced both nc and covalent ( c ) complexes XN' + -(CO 2 ) - . In all such cases, crossover from an nc to c complex is clearly demarcated with the identification of a transition state ( ts ). The complexes XN'···CO 2 and XN' + -(CO 2 ) - are bond stretch isomers, and they define the weak and strong bonding territories, respectively, while the ts appears as the demarcation point of the two territories. Cluster formation of XN with CO 2 reinforces the interaction between them, and all become covalent clusters of general formula (XN + -(CO 2 ) - ) n . The positive cooperativity associated with the NH···OC hydrogen bond formation between any two XN' + -(CO 2 ) - units strengthened the N-C coordinate covalent bond and led to massive stabilization of the cluster. For instance, the stabilizing interaction between the XN unit with CO 2 is increased from 2-7 kcal/mol range in a monomer complex to 14-31 kcal/mol range for the octamer cluster (XN' + -(CO 2 ) - ) 8 . The cooperativity effect compensates for the large reduction in the entropy of cluster formation. Several imine systems showed the exergonic formation of the cluster and are predicted as potential candidates for CO 2 capture and conversion.

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.

Herein, we report a comprehensive study of CO 2 hydroboration catalyzed by Mn pincer complexes. The traditional metal-ligand cooperation (MLC) mechanism based on the H-Mn-N-Bpin pincer complex is not viable due to the competing abstraction of the Bpin group from the H-Mn-N-Bpin complex by NaO t Bu. Instead, we propose an ionic mechanism based on the H-Mn-N-Na species with a low energy span (22.5 kcal/mol) and unveil the acceleration effect of bases. The X groups in the H-Mn-N-X catalyst models are further modulated, and the steric hindrance and H→B donor-acceptor interactions of the X group increase the energy barrier of the hydride transfer. The hydrogen bond and electrostatic interactions of the X group can accelerate the hydride transfer to HCOOBpin and HCHO molecules except for the nonpolar CO 2 molecule. Based on these discoveries, we designed a pyridine-based Mn pincer catalyst system, which could achieve CO 2 hydroboration in low-temperature and base-free conditions through a metal-ligand cooperation mechanism.

Recent advances in quantifying nucleophilic reactivities in chemical reactions and intermolecular interactions of aromatic molecules are reviewed. This survey covers experimental (IR frequency shifts induced by hydrogen bonding) and theoretical (modeling of potential energy surfaces, atomic charges, molecular electrostatic potential) approaches in characterizing chemical reactivity. Recent advances in software developments assisting the evaluation of the reactive sites for electrophilic aromatic substitution are briefly discussed., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Approximating molecular wave functions involves heavy numerical effort; therefore, codes for such tasks are written completely or partially in efficient languages such as C, C++, and Fortran. While these tools are dominant throughout quantum chemistry packages, the efficient development of new methods is often hindered by the complexity associated with code development. In order to ameliorate this scenario, some software packages take a dual approach where a simpler, higher-level language, such as Python, substitutes the traditional ones wherever performance is not critical. Julia is a novel, dynamically typed, programming language that aims to solve this two-language problem. It gained attention because of its modern and intuitive design, while still being highly optimized to compete with "low-level" languages. Recently, some chemistry-related projects have emerged exploring the capabilities of Julia. Herein, we introduce the quantum chemistry package Fermi.jl, which contains the first implementations of post-Hartree-Fock methods written in Julia. Its design makes use of many Julia core features, including multiple dispatch, metaprogramming, and interactive usage. Fermi.jl is a modular package, where new methods and implementations can be easily added to the existing code. Furthermore, it is designed to maximize code reusability by relying on general functions with specialized methods for particular cases. The feasibility of the project is explored through evaluating the performance of popular ab initio methods. It is our hope that this project motivates the usage of Julia within the community and brings new contributions into Fermi.jl.

Dimerizations of fulvene metal tricarbonyl complexes of the type (C 5 H 4 CRR')M(CO) 3 (R, R' = MeO, Me, H; M = Cr, Mo, W) to form a metal-metal bond and a new carbon-carbon bond, thereby giving binuclear cyclopentadienyl metal carbonyl derivatives, are predicted to be thermochemically favored but to have significant activation energies ranging from Δ E = 19 to 42 kcal/mol. However, the introduction of dimethylamino but not methoxy substituents onto the exocyclic carbon atom changes the situation drastically so that the monomers [C 5 H 4 CH(NMe 2 )]M(CO) 3 and [C 5 H 4 C(NMe 2 ) 2 ]M(CO) 3 become strongly thermochemically favored, lying Δ E = 43 kcal/mol (M = W) to 63 kcal/mol (M = Cr) below their corresponding dimers. In such dimethylamino-substituted (fulvene)M(CO) 3 derivatives, the M-C distance to the exocyclic fulvene carbon is lengthened beyond the bonding distance to give a zwitterionic structure with a pentahapto fulvene ligand. Such M-C distances in (fulvene)M(CO) 3 complexes, which have preferred zwitterionic structures, increase with increasing solvent polarity (i.e., dielectric constant) until a saturation point is reached.

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 H 2 , 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(V 5 O 3 ) scaling.

Aluminyl anions are low-valent, anionic, and carbenoid aluminum species commonly found stabilized with potassium cations from the reaction of Al-halogen precursors and alkali compounds. These systems are very reactive toward the activation of σ-bonds and in reactions with electrophiles. Various research groups have detected that the potassium atoms play a stabilization role via electrostatic and cation ⋯ π interactions with nearby (aromatic)-carbocyclic rings from both the ligand and from the reaction with unsaturated substrates. Since stabilizing K⋯H bonds are witnessed in the activation of this class of molecules, we aim to unveil the role of these metals in the activation of the smaller and less polarizable H 2 molecule, together with a comprehensive characterization of the reaction mechanism. In this work, the activation of H 2 utilizing a NON-xanthene-Al dimer, [K{Al(NON)}] 2 (D) and monomeric, [Al(NON)] - (M) complexes are studied using density functional theory and high-level coupled-cluster theory to reveal the potential role of K + atoms during the activation of this gas. Furthermore, we aim to reveal whether D is more reactive than M (or vice versa), or if complicity between the two monomer units exits within the D complex toward the activation of H 2 . The results suggest that activation energies using the dimeric and monomeric complexes were found to be very close (around 33 kcal mol -1 ). However, a partition of activation energies unveiled that the nature of the energy barriers for the monomeric and dimeric complexes are inherently different. The former is dominated by a more substantial distortion of the reactants (and increased interaction energies between them). Interestingly, during the oxidative addition, the distortion of the Al complex is minimal, while H 2 distorts the most, usually over 0.77 Δ E d i s t ≠ . Overall, it is found here that electrostatic and induction energies between the complexes and H 2 are the main stabilizing components up to the respective transition states. The results suggest that the K + atoms act as stabilizers of the dimeric structure, and their cooperative role on the reaction mechanism may be negligible, acting as mere spectators in the activation of H 2 . Cooperation between the two monomers in D is lacking, and therefore the subsequent activation of H 2 is wholly disengaged., (© 2021 Wiley-VCH GmbH.)

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 (AlH 2 - ) 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.

Four different reaction pathways are initially located for the reaction of Cl atom plus water trimer Cl + (H 2 O) 3 → HCl + (H 2 O) 2 OH using a standard DFT method. As found for the analogous fluorine reaction, the geometrical and energetic results for the four chlorine pathways are closely related. However, the energetics for the Cl reaction are very different from those for fluorine. In the present paper, we investigate the lowest-energy chlorine pathway using the "gold standard" CCSD(T) method in conjunction with correlation-consistent basis sets up to cc-pVQZ. Structurally, the stationary points for the water trimer reaction Cl + (H 2 O) 3 may be compared to those for the water monomer reaction Cl + H 2 O and water dimer reaction Cl + (H 2 O) 2 . Based on the CCSD(T) energies, the title reaction is endothermic by 19.3 kcal mol -1 , with a classical barrier height of 16.7 kcal mol -1 between the reactants and the exit complex. There is no barrier for the reverse reaction. The Cl⋯(H 2 O) 3 entrance complex lies 5.3 kcal mol -1 below the separated reactants. The HCl⋯(H 2 O) 2 OH exit complex is bound by 8.6 kcal mol -1 relative to the separated products. The Cl + (H 2 O) 3 reaction is somewhat similar to the analogous Cl + (H 2 O) 2 reaction, but qualitatively different from the Cl + H 2 O reaction. It is reasonable to expect that the reactions between the chlorine atom and larger water clusters may be similar to the Cl + (H 2 O) 3 reaction. The potential energy profile for the Cl + (H 2 O) 3 reaction is radically different from that for the valence isoelectronic F + (H 2 O) 3 system, which may be related to the different bond energies between HCl and HF.

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.

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.

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 (ΔE ST =E Singlet -E Triplet ) 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-PH 2 (-3.2 kcal mol -1 ) and P-NH 2 (-0.2 kcal mol -1 ). ΔE ST 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 ΔE ST of fundamental Pn-R moieties and provides a firm foundation for the continued study of heavier pnictinidenes., (© 2021 Wiley-VCH GmbH.)

A series of reactions between Lewis bases and an imidazole-based dithione dimer (1) has been investigated. Both cyclic(alkyl)(amino)carbene (CAAC) (2) and N-heterocyclic carbene (NHC) (4), in addition to N-heterocyclic silylene (NHSi) (6), demonstrate the capability to cleave the sulphur-sulphur bonds in 1, giving carbene-stabilized dithiolene (L 0 ) zwitterions (3 and 5) and a spirocyclic silicon-dithiolene compound (7), respectively. The bonding nature of 3, 5, and 7 are probed by both experimental and theoretical methods., (© 2021 Wiley-VCH GmbH.)

In 2019, Diaz-Urrutia and Ott developed a high-yield method for direct conversion of methane to methanesulfonic acid and proposed a cationic chain reaction mechanism. However, Roytman and Singleton questioned this mechanism, and they favored a free-radical mechanism. In the present paper, we studied both the cationic chain and radical mechanisms and found the radical mechanism is more favorable, since it has a much lower energy barrier. However, the radical mechanism has not considered the effect of ions for the reaction taking place in oleum. Thus, we studied a simple model of a protonated radical mechanism, which further lowers the energy barrier. Although the true mechanism for the CH 4 + SO 3 reaction could be more complicated in electrolyte solutions, this model should be helpful for the further study of the mechanism of this reaction.

Important recent experimental studies have allowed the isomer-selective identification of the 2-, 3-, and 4-picolyl radicals. The picolyl radicals and their valence isoelectronic P, As, Sb, and Bi congeners are investigated here. For the three observed parent radicals, the theoretical ionization potentials agree with experiment to within 0.02 eV. Two rules are proposed for predicting vertical ionization potentials ( E VIE ) and relative energies. The E VIE values for these radicals will be higher when large percentages of the SOMO orbitals are distributed on the atoms with greater electronegativities. The cations of these systems were also studied along with the closed-shell methylpyridines and their P, As, Sb, and Bi analogs. The energies for the cationic species will lie lower when high percentages of π natural localized molecular orbitals occur on the more electronegative atoms. The structures of the 2- and 4-isomers strongly depend upon the heteroatoms, with the C-C linkages adopting a single-double alternating bond manner when the heteroatoms become heavier. The 3-isomers adopt roughly equal C-C bond distances with small changes from N to Bi.