New global minimum conformers for the Pt and Pt clusters: low symmetric species featuring different active sites.

Context: The study of platinum (Pt) clusters and nanoparticles is essential due to their extensive range of potential technological applications, particularly in catalysis. The electronic properties that yield optimal catalytic performance at the nanoscale are significantly influenced by the size and structure of Pt clusters. This research aimed to identify the lowest-energy conformers for Pt , Pt , and Pt species using Density Functional Theory (DFT).

Does Aromaticity Play a Role in Electronic and Structural Properties of YB (n=2-14) Clusters?

Nanoclusters exhibit electronic, optical, and magnetic properties that differ significantly from those of extended and molecular systems with comparable stoichiometries. In this work, we examined the structural, energetic, and electronic characteristics of yttrium-doped boron clusters (YB, where n ranges from 2 to 14) with the aid of robust wavefunction analysis tools. Special emphasis is placed on the elucidation of the potential aromatic character exhibited by the resultant molecules and how it can affect their chemical bonding and stability.

Radical revelations: the pnictogen effect in linear acetylenes.

Acetylenes are essential building blocks in modern chemistry due to their remarkable modularity. The introduction of heteroatoms, such as pnictogens (X), is one of the simplest approaches to altering the C≡C bond. However, the chemistry of the resultant dipnictogenoacetylenes (DXAs) is strongly dependent on the nature of X.

Synthesis of Functionalized Tetrasubstituted Allenes by the Addition of Bis(trimethylsilyl)ketene Acetals to Ynones Catalyzed by Gold(I).

We have developed a straightforward and rapid methodology for the synthesis of tetrasubstituted allenes bearing carboxylic acids in the 1,3-position through the gold(I)-catalyzed nucleophilic addition of bis(trimethylsilyl)ketene acetals to ynones. The reaction was evaluated with several substrates, and 21 allenes were obtained in moderate to good yields. Using DFT calculations, we studied the mechanism of the reaction, which suggested a nucleophilic 1,4-addition pathway.

On the structure and electronic properties of Pt clusters: new most stable structures for = 16-17.

The lowest energy structures and electronic properties of Pt clusters up to = 17 are investigated by using a genetic algorithm in combination with density functional theory calculations. There are several putative global minimum structures for platinum clusters which have been reported by using different approaches, but a comprehensive study for = 15-17 has not been carried out so far. Herein, we perform a consensus using GGA (PBE), meta-GGA (TPSS) and hybrid (B3PW91, PBE0, PBEh-3c, M06-L) functionals in conjunction with the Def2-TZVP basis set.

Wave function analyses of scandium-doped aluminium clusters, AlnSc ( = 1-24), and their CO fixation abilities.

Nanoclusters represent a connection between (i) solid state systems and (ii) species in the atomic and molecular domains. Additionally, nanoclusters can also have very interesting electronic, optical and magnetic properties. For example, some aluminium clusters behave as superatoms and the doping of these clusters might strengthen their adsorption capabilities.

Atoms in molecules in real space: a fertile field for chemical bonding.

In this perspective, we review some recent advances in the concept of atoms-in-molecules from a real space perspective. We first introduce the general formalism of atomic weight factors that allows unifying the treatment of fuzzy and non-fuzzy decompositions under a common algebraic umbrella. We then show how the use of reduced density matrices and their cumulants allows partitioning any quantum mechanical observable into atomic or group contributions.

A QCT View of the Interplay between Hydrogen Bonds and Aromaticity in Small CHON Derivatives.

The somewhat elusive concept of aromaticity plays an undeniable role in the chemical narrative, often being considered the principal cause of the unusual properties and stability exhibited by certain π skeletons. More recently, the concept of aromaticity has also been utilised to explain the modulation of the strength of non-covalent interactions (NCIs), such as hydrogen bonding (HB), paving the way towards the in silico prediction and design of tailor-made interacting systems. In this work, we try to shed light on this area by exploiting real space techniques, such as the Quantum Theory of Atoms in Molecules (QTAIM), the Interacting Quantum Atoms (IQA) approaches along with the electron delocalisation indicators Aromatic Fluctuation (FLU) and Multicenter (MCI) indices.

Binding Energy Partition of Promising IRAK-4 Inhibitor (Zimlovisertib) for the Treatment of COVID-19 Pneumonia.

The technique of Fragment-Based Drug Design (FBDD) considers the interactions of different moieties of molecules with biological targets for the rational construction of potential drugs. One basic assumption of FBDD is that the different functional groups of a ligand interact with a biological target in an approximately additive, that is, independent manner. We investigated the interactions of different fragments of ligands and Interleukin-1 Receptor-Associated Kinase 4 (IRAK-4) throughout the FBDD design of Zimlovisertib, a promising anti-inflammatory, currently in trials to be used for the treatment of COVID-19 pneumonia.

Partition of the electronic energy of the PM7 method the interacting quantum atoms approach.

Partitions of the electronic energy such as that provided by the Interacting Quantum Atoms (IQA) approach have given valuable insights for numerous chemical systems and processes. Unfortunately, this kind of analysis may involve the integration of scalar fields over very irregular volumes, a condition which leads to a large and often prohibitive computational effort. These circumstances have limited the use of these energy partitions to systems comprising a few tens of atoms at most.

Understanding the effect of mechanical strains on the catalytic activity of transition metals.

The effect of elastic strains on the catalytic activity for the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) was analyzed on thirteen late transition metals: eight (111) surfaces of fcc metals (Ni, Cu, Pd, Ag, Pt, Au, Rh, Ir) and five (0001) surfaces of hcp metals (Co, Zn, Cd, Ru, and Os). The corresponding adsorption energies for the different intermediate reactions up to strains dictated by the mechanical stability limits were previously obtained by means of density functional theory calculations. It was found that the elastic strains can be used to tune the catalytic activity of different metals by reducing the energy barrier of the rate limiting step and even to reach the cusp of the volcano plot.

NNAIMQ: A neural network model for predicting QTAIM charges.

Atomic charges provide crucial information about the electronic structure of a molecular system. Among the different definitions of these descriptors, the one proposed by the Quantum Theory of Atoms in Molecules (QTAIM) is particularly attractive given its invariance against orbital transformations although the computational cost associated with their calculation limits its applicability. Given that Machine Learning (ML) techniques have been shown to accelerate orders of magnitude the computation of a number of quantum mechanical observables, in this work, we take advantage of ML knowledge to develop an intuitive and fast neural network model (NNAIMQ) for the computation of QTAIM charges for C, H, O, and N atoms with high accuracy.

Stronger-together: the cooperativity of aurophilic interactions.

Crystallographic distances and the electron density of bi- and tri-nuclear gold(I) compounds reveal that the existence of multiple Au⋯Au interactions increases their individual strength in the order of 0.9-2.9 kcal mol.

The effect of elastic strains on the adsorption energy of H, O, and OH in transition metals.

The influence of elastic strains on the adsorption of H, O, and OH on the (111) surfaces of 8 fcc (Ni, Cu, Pd, Ag, Pt, Au, Rh, Ir) and on the (0001) surfaces of 3 hcp (Co, Zn, Cd) transition metals was analyzed by means of density functional theory calculations. To this end, surface slabs were subjected to different strain states (uniaxial, biaxial, shear, and a combination of them) up to strains dictated by the mechanical stability limits indicated by phonon calculations. It was found that the adsorption energy followed the predictions of the d-band theory but - surprisingly - the variations in the adsorption energy only depended on the area of the adsorption hole and not on the particular elastic strain tensor applied to achieve this area.

On the Relationship between Hydrogen Bond Strength and the Formation Energy in Resonance-Assisted Hydrogen Bonds.

Resonance-assisted hydrogen bonds (RAHB) are intramolecular contacts that are characterised by being particularly energetic. This fact is often attributed to the delocalisation of π electrons in the system. In the present article, we assess this thesis via the examination of the effect of electron-withdrawing and electron-donating groups, namely -F, -Cl, -Br, -CF, -N(CH), -OCH, -NHCOCH on the strength of the RAHB in malondialdehyde by using the Quantum Theory of Atoms in Molecules (QTAIM) and the Interacting Quantum Atoms (IQA) analyses.

The nature of the intermolecular interaction in (HX) (X = O, S, Se).

Hydrogen bonds (HBs) are crucial non-covalent interactions in chemistry. Recently, the occurrence of an HB in (H2S)2 has been reported (Arunan et al., Angew.

Cooperativity and Anticooperativity in Ion-Water Interactions: Implications for the Aqueous Solvation of Ions.

Non-additive effects in hydrogen bonds (HB) take place as a consequence of electronic charge transfers. Therefore, it is natural to expect cooperativity and anticooperativity in ion-water interactions. Nevertheless, investigations on this matter are scarce.

Photochemistry in Real Space: Batho- and Hypsochromism in the Water Dimer.

Invited for the cover of this issue is Alberto Fernández-Alarcón and co-workers at The Institute of Chemistry of the National Autonomous University of Mexico and The School of Chemistry of the University of Oviedo. The image depicts the real space analysis of the excitation energies in the double blue and red shift of the water dimer. Read the full text of the article at 10.

Interacting Quantum Atoms-A Review.

The aim of this review is threefold. On the one hand, we intend it to serve as a gentle introduction to the Interacting Quantum Atoms (IQA) methodology for those unfamiliar with it. Second, we expect it to act as an up-to-date reference of recent developments related to IQA.

Photochemistry in Real Space: Batho- and Hypsochromism in the Water Dimer.

The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born-Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H O) . It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism.

On the strength of hydrogen bonding within water clusters on the coordination limit.

Hydrogen bonds (HB) are arguably the most important noncovalent interactions in chemistry. We study herein how differences in connectivity alter the strength of HBs within water clusters of different sizes. We used for this purpose the interacting quantum atoms energy partition, which allows for the quantification of HB formation energies within a molecular cluster.

Directing the Crystal Packing in Triphenylphosphine Gold(I) Thiolates by Ligand Fluorination.

We explore herein the supramolecular interactions that control the crystalline packing in a series of fluorothiolate triphenylphosphine gold(I) compounds with the general formula [Au(SR)(PhP)] in which PhP = triphenylphosphine and SR = SCF, SCHF-4, SCF(CF)-4, SCHF-2,4, SCHF-3,4, SCHF-3,5, SCH(CF)-2, SCHF-2, SCHF-3, SCHF-4, SCF, and SCHCF. We use for this purpose (i) DFT electronic structure calculations and (ii) the quantum theory of atoms in molecules and the non-covalent interactions index methods of wave function analyses. Our combined experimental and computational approach yields a general understanding of the effects of ligand fluorination in the crystalline self-assembly of the examined systems, in particular, about the relative force of aurophilic contacts compared with other supramolecular interactions.

Efficient implementation of the interacting quantum atoms energy partition of the second-order Møller-Plesset energy.

We describe an efficient implementation of the partition of the second-order Møller-Plesset (MP2) correlation energy within the interacting quantum atoms (IQA) energy decomposition. We simplify the IQA integration bottleneck by considering only the occupied to virtual elements of the second order reduced density matrix, a procedure that reduces substantially the size of the two-electron matrix, which has to be addressed. The algorithmic improvements described herein allow to perform the decomposition of the MP2 correlation energy for medium size molecular systems using moderate computational resources.

Exotic Bonding Regimes Uncovered in Excited States.

Real-space tools were employed to show that the chemical bonding scenario used routinely to understand ground states lacks the necessary flexibility in excited states. It is shown that, even for two-center, two-electron bonds, the real-space bond orders have exotic values that have never been reported. The nature of these situations was uncovered by using electron-counting techniques that provide an appealing statistical interpretation of bonding descriptors, together with simple physical models.

Partition of electronic excitation energies: the IQA/EOM-CCSD method.

Different developments in chemistry and emerging technologies have generated a renewed interest in the properties of molecular excited states. We present herein the partition of black-box, size-consistent equation-of-motion coupled cluster singles and doubles (EOM-CCSD) excitation energies within the framework of the interacting quantum atoms (IQA) formalism. We denote this method as IQA/EOM-CCSD.