Thiocarbonyl Pseudohalides - The Curious Case of Thiocarbonyl Dithiocyanate.

Thiocarbonyl dithiocyanate (1) and chlorothiocarbonyl thiocyanate (2) were synthesized from thiophosgene and ammonium or silver thiocyanate, respectivley. Their crystal structures show syn-anti (1) and syn (2) conformations, which were confirmed in the bulk phases by powder X-ray diffraction, vibrational spectroscopy and DFT calculations. Further calculations explain the isolation of the kinetic reaction products by a lower transition states opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof-of-principle study we show that it in turn can be used for the complexation of nickel to yield (4).

Isomer-Dependent Escape Rate of Xenon from a Water-Soluble Cryptophane Cage Studied by Ab Initio Molecular Dynamics.

The escape of xenon from the anti and syn diastereomers of hexacarboxylic-cryptophane-222 in water has been studied by ab initio molecular dynamics simulations. The structures of both complexes, when the xenon atom is trapped inside their cages, have been compared and show no major differences. The free-energy profiles corresponding to the escape reaction have been calculated with the Blue Moon ensemble method using the distance between Xe and the center of mass of the cage as the reaction coordinate. The resulting free-energy barriers are very different; the escape rate is much faster in the case of the syn diastereomer, in agreement with experimental data obtained in hyperpolarized 129 Xe NMR. Our simulations reveal the mechanistic details for each diastereomer and provide an explanation for the different in-out xenon rates based on the solvation structure around the cages.

Theoretical Rotational and Vibrational Spectral Data for the Hypermagnesium Oxide Species Mg2O and Mg2O.

While magnesium is astronomically observed in small molecules, it largely serves as a contributor to silicate grains, though how these grains form is not well-understood. The smallest hypermagnesium oxide compounds (Mg 2 ${{}_{2}}$ O/Mg 2 ${{}_{2}}$ O + ${{}^{+}}$ ) may play a role in silicate formation, but little vibrational reference data exist. As such, anharmonic spectroscopic data are computed for X ˜ 1 Σ g + ${{{\tilde{\rm {X}}}}^1 {\rm{\Sigma }}_g^+ }$ Mg 2 ${{}_{2}}$ O, a ˜ 1 Σ u + ${{{\tilde{\rm {a}}}}^1 {\rm{\Sigma }}_u^+ }$ Mg 2 ${{}_{2}}$ O, and X ˜ 2 Σ g + ${{{\tilde{\rm {X}}}}^2 {\rm{\Sigma }}_g^+ }$ Mg 2 ${{}_{2}}$ O + ${{}^{+}}$ using quartic force fields (QFFs). Explicitly-correlated coupled-cluster QFFs for the neutral species perform well, implying that full multireference treatment may not be necessary for such systems if enough electron correlation is included. Equation-of-motion ionization potential (EOMIP) methods for X ˜ 2 Σ g + ${{{\tilde{\rm {X}}}}^2 {\rm{\Sigma }}_g^+ }$ Mg 2 ${{}_{2}}$ O + ${{}^{+}}$ QFFs circumvent previous symmetry breaking issues even in explicitly-correlated coupled-cluster results, motivating the need for EOMIP treatments at minimum for such systems. All three species are found to have high-intensity vibrational frequencies. Even so, the highly intense frequency ( X ˜ 1 Σ g + ${{{\tilde{\rm {X}}}}^1 {\rm{\Sigma }}_g^+ }$ Mg 2 ${{}_{2}}$ O: 894.7 cm-1/11.18 µm; a ˜ 1 Σ u + ${{{\tilde{\rm {a}}}}^1 {\rm{\Sigma }}_u^+ }$ Mg 2 ${{}_{2}}$ O: 915.0 cm-1/10.91 µm) for either neutral state may be astronomically obscured by the polycyclic aromatic hydrocarbon 11.2 µm band. Mg 2 ${{}_{2}}$ O + ${{}^{+}}$ may be less susceptible to such obfuscation, and its ν 1 ${{\nu }_{1}}$ intensity is computed to be a massive 4793 km mol-1.

Tuning (Anti)Aromaticity: Variations on the [8]-Circulene Framework.

Optoelectronic properties of organic molecules are underpinned by delocalisation and delocalisability of π-electrons. These properties are sensitive to small changes in electron count, whether achieved by heteroatom substitution or redox chemistry. One measure of the delocalisability of π-electrons is the current induced by an external magnetic field, which is diagnostic of (anti)aromaticity. The ab initio ipsocentric method is used here to model diverse ring-current patterns in the family of [8]-circulenes based on tetracyclopenta[def,jkl,pqr,vwx]tetraphenylene (TCPTP), in different charge states, with disjoint hetero-atom substitution, and with CC units systematically replaced by BN pairs. Maps calculated at the CHF/CTOCD-DZ2/6-31G** level reveal that these modifications of the TCPTP framework access the full range of possibilities for current from concentric global circulations (typically counter rotating) to full (non-aromatic) localisation. In the ipsocentric approach, induced current density is partitioned into robust orbital contributions that obey selection rules based on orbital symmetry, energy and nodal character. The selection rules are applied here to interpret current-density and exploit insights gained from simpler models to suggest design strategies for fine-tuning of π-delocalisability (aromaticity and antiaromaticity) in macrocyclic frameworks.

A nuclear configuration interaction approach to study nuclear spin effects: an application to ortho- and para-3 He2 @C60.

We introduce a non-orthogonal configuration interaction approach to investigate nuclear quantum effects on energies and densities of confined fermionic nuclei. The Hamiltonian employed draws parallels between confined systems and many-electron atoms, where effective non-Coulombic potentials represent the interactions of the trapped particles. One advantage of this method is its generality, as it offers the potential to study the nuclear quantum effects of various confined species affected by effective isotropic or anisotropic potentials. As a first application, we analyze the quantum states of two 3 He atoms encapsulated in C60 . At the Hartree-Fock level, we observe the breaking of spin and spatial symmetries. To ensure wavefunctions with the correct symmetries, we mix the broken-symmetry Hartree-Fock states within the non-orthogonal configuration interaction expansion. Our proposed approach predicts singly and triply degenerate ground states for the singlet (para-3 He2 @C60 ) and triplet (ortho-3 He2 @C60 ) nuclear spin configurations, respectively. The ortho-3 He2 @C60 ground state is 5.69 cm-1 higher in energy than the para-3 He2 @C60 ground state. The nuclear densities obtained for these states exhibit the icosahedral symmetry of the C60 embedding potential. Importantly, our calculated energies for the lowest 85 states are in close agreement with perturbation theory results based on a harmonic oscillator plus rigid rotor model of 3 He2 @C60 .

Dispersion-Driven Cooperativity in Alkyl Perylene Diimide Oligomers: Insights from Density Functional Theory.

The cooperative mechanism is of paramount importance in the synthesis of supramolecular polymers with desired characteristics, including molecular mass, polydispersity, and morphology. It is primarily driven by the presence of intermolecular interactions, which encompass strong hydrogen bonding, metal-ligand interactions, and dipole-dipole interactions. In this study, we utilize density functional theory and energy decomposition analysis to investigate the cooperative behavior of perylene diimide (PDI) oligomers with alkyl chains at their imide positions, which lack the previously mentioned interactions. Our systematic examination reveals that dispersion interactions originating from the alkyl side-chain substituents play an important role in promoting cooperativity within these PDIs. This influence becomes even more pronounced for alkyl chain lengths beyond hexyl groups. The energy decomposition analysis reveals that the delicate balance between dispersion energy and Pauli repulsion energy is the key driver of cooperative behavior in PDIs. Additionally, we have developed a mathematical model capable of predicting the saturated binding energies for PDI oligomers of varying sizes and alkyl chain lengths. Overall, our findings emphasize the previously undervalued significance of dispersion forces in cooperative supramolecular polymerization, enhancing our overall understanding of the cooperative mechanism.

Elevating the Performance of Heterometallic 3d/4f SMMs: The Role of Diamagnetic CoIII and ZnII Ions in Magnetization Dynamics.

Recent advances in the synthesis of 3d/4f Single-Molecule Magnets (SMMs) have revealed the effective role of incorporating diamagnetic CoIII or ZnII ions to enhance the magnetic properties of LnIII ions. This concept highlights notable examples of CoIII/LnIII and ZnII/LnIII SMMs documented in the recent literature, illustrating how the selection of various peripheral and/or bridging ligands can modulate the magnetic anisotropy of 4f metal ions, thereby increasing their energy barriers.

In silico Investigation of the Thermochemistry and Photoactivity of Pyruvic Acid in an Aqueous Solution of NaCl.

The photochemistry of oxocarboxylic acids contributes significantly to the complex chemistry occurring in the atmosphere. In this regard, pyruvic acid undergoes photoreactions that lead to many diverse products. The presence of sodium cation near pyruvic acid in an aqueous solution, or its conjugate base in non-acidic conditions, influences the hydration equilibrium and the photosensitivity to UV-visible light of the oxocarboxylic acid. We performed an ab initio metadynamics simulation which serves two purposes: first, it unveils the mechanisms of the reversible hydration reaction between the keto and the diol forms, with a free-energy difference of only 2 kJ/mol at 300 K, which shows the influence of sodium on the keto/diol ratio; second, it provides solvent-shared ion pairing (SSIP) and contact ion pairing (CIP) structures, including Na+ coordinated to carbonyl, for the calculations of the electronic transition energies to an antibonding π* orbital, which sheds light on the photoactivity of these two forms in the actinic region.

Hydrogen Bonding versus Halogen Bonding: Spectroscopic Investigation of Gas-Phase Complexes Involving Bromide and Chloromethanes.

Hydrogen bonding and halogen bonding are important non-covalent interactions that are known to occur in large molecular systems, such as in proteins and crystal structures. Although these interactions are important on a large scale, studying hydrogen and halogen bonding in small, gas-phase chemical species allows for the binding strengths to be determined and compared at a fundamental level. In this study, anion photoelectron spectra are presented for the gas-phase complexes involving bromide and the four chloromethanes, CH3 Cl, CH2 Cl2 , CHCl3 , and CCl4 . The stabilisation energy and electron binding energy associated with each complex are determined experimentally, and the spectra are rationalised by high-level CCSD(T) calculations to determine the non-covalent interactions binding the complexes. These calculations involve nucleophilic bromide and electrophilic bromine interactions with chloromethanes, where the binding motifs, dissociation energies and vertical detachment energies are compared in terms of hydrogen bonding and halogen bonding.

Relativistic Density Functional NMR Tensors Analyzed with Spin-free Localized Molecular Orbitals.

The implementation of fast relativistic methods based on density functional theory, in conjunction with localized molecular orbital (LMO) based analysis, allows straightforward interpretations of NMR parameters in terms of contributions from core shells, lone pairs, and bonds, for compounds containing elements from across the periodic table. We present a conceptual review of a frequently used LMO analysis of NMR parameters calculated in the presence of spin-orbit interactions and other relativistic effects. An accompanying example focuses on the 15 N shielding in a heavy metal complex.

Photochemical Reaction Mechanism of Intramolecular H Transfer Reaction of H2 C3 O+ ⋠Radical Cation.

The photochemical reaction mechanism underlying the intramolecular H-transfer of the H2 C3 O+ ⋅ radical cation to the H2 CCCO+ ⋅ methylene ketene cation was elucidated using time-dependent density functional theory and high-level ab initio methods. Once the D1 state of H2 C3 O+ ⋅ is populated, the reaction proceeds to form an intermediate (IM) in the D1 state (IM4D1 ). The molecular structure of the conical intersection (CI) was optimized using a multiconfigurational ab initio method. The CI is readily accessible because it lies slightly above the IM4D1 in energy. In addition, the gradient difference vector of the CI is almost parallel to the intramolecular H-transfer reaction coordinate. Once the vibration mode of IM4D1 which is parallel to the reaction coordinate is populated, the degeneracy of the CI is readily lifted and H2 CCCO+ ⋅ was formed via a relaxation pathway in the D0 state. Our calculated results clearly describe the photochemical intramolecular H transfer reaction reported in a recent study.

Mixed-Valence Compounds as Polarizing Agents for Overhauser Dynamic Nuclear Polarization in Solids*.

Herein, we investigate a novel set of polarizing agents-mixed-valence compounds-by theoretical and experimental methods and demonstrate their performance in high-field dynamic nuclear polarization (DNP) NMR experiments in the solid state. Mixed-valence compounds constitute a group of molecules in which molecular mobility persists even in solids. Consequently, such polarizing agents can be used to perform Overhauser-DNP experiments in the solid state, with favorable conditions for dynamic nuclear polarization formation at ultra-high magnetic fields.

Assessing the Viability of the Methylsulfinyl Radical-Ozone Reaction.

Although integral to remote marine atmospheric sulfur chemistry, the reaction between methylsulfinyl radical (CH3 SO) and ozone poses challenges to theoretical treatments. The lone theoretical study on this reaction reported an unphysically large barrier of 66 kcal mol-1 for abstraction of an oxygen atom from O3 by CH3 SO. Herein, we demonstrate that this result stems from improper use of MP2 with a single-reference, unrestricted Hartree-Fock (UHF) wavefunction. We characterized the potential energy surface using density functional theory (DFT), as well as multireference methodologies employing a complete active-space self-consistent field (CASSCF) reference. Our DFT PES shows, in contrast to previous work, that the reaction proceeds by forming an addition adduct [CH3 S(O3 )O] in a deep potential well of 37 kcal mol-1 . An O-O bond of this adduct dissociates via a flat, low barrier of 1 kcal mol-1 to give CH3 SO2 +O2 . The multireference computations show that the initial addition of CH3 SO+O3 is barrierless. These results provide a more physically intuitive and accurate picture of this reaction than the previous theoretical study. In addition, our results imply that the CH3 SO2 formed in this reaction can readily decompose to give SO2 as a major product, in alignment with the literature on CH3 SO reactions.

Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab†Initio Approach.

Lithium phosphorus oxynitride (LiPON) is an amorphous solid-state lithium ion conductor displaying exemplary cyclability against lithium metal anodes. There is no definitive explanation for this stability due to the limited understanding of the structure of LiPON. Herein, we provide a structural model of RF-sputtered LiPON. Information about the short-range structure results from 1D and 2D solid-state NMR experiments. These results are compared with first principles chemical shielding calculations of Li-P-O/N crystals and ab initio molecular dynamics-generated amorphous LiPON models to unequivocally identify the glassy structure as primarily isolated phosphate monomers with N incorporated in both apical and as bridging sites in phosphate dimers. Structural results suggest LiPON's stability is a result of its glassy character. Free-standing LiPON films are produced that exhibit a high degree of flexibility, highlighting the unique mechanical properties of glassy materials.

Planting Repulsion Centers for Faster Ionic Diffusion in Superionic Conductors.

The successful launch of solid-state batteries relies on the discovery of solid electrolytes with remarkably high ionic conductivity. Extensive efforts have identified several important superionic conductors (SICs) and broadened our understanding of their superionic conductivity. Herein, we propose a new design strategy to facilitate ionic conduction in SICs by planting immobile repulsion centers. Our ab initio molecular dynamics simulations on the model system Na11 Sn2 PS12 demonstrate that the sodium ionic conductivity can be increased by approximately one order of magnitude by simply doping large Cs ions as repulsion centers in the characteristic vacant site of Na11 Sn2 PS12 . Planting immobile repulsion centers locally induces the formation of high-energy sites, leading to a fast track for ionic conduction owing to the unique interactions among mobile ions in SICs. Seemingly non-intuitive approaches tailor the ionic diffusion by exploiting these immobile repulsion centers.

Spodium Bonds: Noncovalent Interactions Involving Group†12 Elements.

The term spodium (Sp) bond is proposed to refer to a net attractive interaction between any element of Group 12 and electron-rich atoms (Lewis bases or anions). These noncovalent interactions are markedly different from coordination bonds (antibonding Sp-ligand orbital involved). Evidence is provided for the existence of this interaction by calculations at the RI-MP2/aug-cc-pVTZ level of theory, atoms-in-molecules, and natural bond orbital analyses and by examining solid-state structures in the Cambridge Structure Database.

Computational Prediction of 1 H and 13 C NMR Chemical Shifts for Protonated Alkylpyrroles: Electron Correlation and Not Solvation is the Salvation.

Prediction of chemical shifts in organic cations is known to be a challenge. In this article we meet this challenge for α-protonated alkylpyrroles, a class of compounds not yet studied in this context, and present a combined experimental and theoretical study of the 13 C and 1 H chemical shifts in three selected pyrroles. We have investigated the importance of the solvation model, basis set, and quantum chemical method with the goal of developing a simple computational protocol, which allows prediction of 13 C and 1 H chemical shifts with sufficient accuracy for identifying such compounds in mixtures. We find that density functional theory with the B3LYP functional is not sufficient for reproducing all 13 C chemical shifts, whereas already the simplest correlated wave function model, Møller-Plesset perturbation theory (MP2), leads to almost perfect agreement with the experimental data. Treatment of solvent effects generally improves the agreement with experiment to some extent and can in most cases be accomplished by a simple polarizable continuum model. The only exception is the NH proton, which requires inclusion of explicit solvent molecules in the calculation.

t-Si64 : A Novel Silicon Allotrope.

Utilizing first principle calculations, a novel Si64 silicon allotrope in the I41 /amd space group with tetragonal symmetry (denoted as t-Si64 below) is proposed in this work. In addition, also its structural, anisotropic mechanical, and electronic properties along with its minimum thermal conductivity κmin were predicted. The mechanical and thermodynamic stability of t-Si64 were evaluated by means of elastic constants and phonon spectra. The electronic band structure indicates that t-Si64 is an indirect band gap semiconductor with a band gap: 0.67 eV (primitive cell) compared to a direct band gap of 0.70 eV with respect to a conventional cell. The minimum thermal conductivity of t-Si64 (0.74 W cm-1 K-1 ) is much smaller than that of diamond silicon (1.13 W cm-1 K-1 ). Therefore, Si-Ge alloys in the I41 /amd space group are potential thermoelectric materials.

Balancing Donor-Acceptor and Dispersion Effects in Heavy Main Group Element π Interactions: Effect of Substituents on the Pnictogen⋠⋠⋠π Arene Interaction.

High-level ab initio calculations using the DLPNO-CCSD(T) method in conjunction with the local energy decomposition (LED) were performed to investigate the nature of the intermolecular interaction in bismuth trichloride adducts with π arene systems. Special emphasis was put on the effect of substituents in the aromatic ring. For this purpose, benzene derivatives with one or three substituents (R=NO2 , CF3 , OCHO, OH, and NH2 ) were chosen and their influence on donor-acceptor interaction as well as on the overall interaction strength was examined. Local energy decomposition was performed to gain deeper insight into the composition of the interaction. Additionally, the study was extended to the intermolecular adducts of arsenic and antimony trichloride with benzene derivatives having one substituent (R=NO2 and NH2 ) in order to rationalize trends in the periodic table. The analysis of natural charges and frontier molecular orbitals shows that donor-acceptor interactions are of π→σ* type and that their strength correlates with charge transfer and orbital energy differences. An analysis of different bonding motifs (Bi⋅⋅⋅π arene, Bi⋅⋅⋅R, and Cl⋅⋅⋅π arene) shows that if dispersion and donor-acceptor interaction coincide as the donor highest occupied molecular orbital (HOMO) of the arene is delocalized over the π system, the M⋅⋅⋅π arene motif is preferred. If the donor HOMO is localized on the substituent, R⋅⋅⋅π arene bonding motifs are preferred. The Cl⋅⋅⋅π arene bonding motif is the least favorable with the lowest overall interaction energy.

Understanding Regium Bonds and their Competition with Hydrogen Bonds in Au2 :HX Complexes.

A theoretical study of the regium and hydrogen bonds (RB and HB, respectively) in Au2 :HX complexes has been carried out by means of CCSD(T) calculations. The theoretical study shows as overall outcome that in all cases the complexes exhibiting RB are more stable that those with HB. The binding energies for RB complexes range between -24 and -180 kJ ⋅ mol-1, whereas those of the HB complexes are between -6 and -19 kJ ⋅ mol-1 . DFT-SAPT also indicated that HB complexes are governed by electrostatics, but RB complexes present larger contribution of the induction term to the total attractive forces. 197 Au chemical shifts have been calculated using the relativistic ZORA Hamiltonian.