Article
Chemistry, Multidisciplinary
Chao He, Ralf I. Kaiser, Wenchao Lu, Musahid Ahmed, Yahaira Reyes, Stanislaw F. Wnuk, Alexander M. Mebel
Summary: The gas-phase reaction between the 1-indenyl radical and the cyclopentadienyl radical was studied using synchrotron-based mass spectrometry coupled with a pyrolytic reactor. The isomer selective production of phenanthrene, anthracene, and benzofulvalene was identified through soft photoionization with tunable vacuum ultraviolet photons. Our findings challenge the classical theory regarding the combination of radicals and provide insight into the evolution of the cosmic carbon budget.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Qingqing Yang, Qingzhong Li, Steve Scheiner
Summary: The study uses ab initio calculations to investigate the ability of B atoms on different molecules to form noncovalent diboron bonds, finding that certain combinations result in stronger diboron bonds with a higher degree of covalent character due to charge transfer.
Review
Chemistry, Inorganic & Nuclear
Dev Raj, Sumanta Kumar Padhi
Summary: This study focuses on the rarely observed phenomenon of a pyridine bridge covering transition metal ions to form complexes of varying geometry and nuclearity. Approximately 37 discrete coordination complexes with different stereochemical properties were interpreted and studied using Single-Crystal X-Ray Crystallography. These complexes have been utilized for pharmacological and biological activities, as well as in the field of catalysis and magnetochemical studies.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Inorganic & Nuclear
Christina Rowland, Eamonn F. Healy
Summary: This article investigates the utility of topological analysis of electron density in molecules with bridging hydrogens for the detection and characterization of multi-center bonding. By performing DFT calculations to generate electron density for experimental structures of complexes with bridging hydrogens, analysis using the Atoms in Molecules perspective and various indicators and functions reveals a deeper understanding of the nature and complexity of chemical bonds.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Slawomir J. Grabowski
Summary: Structures with trigonal coordination of gallium center interacting with electron rich carbon sites are examined. These interactions, classified as Ga···C triel bonds, are scrutinized for their properties and potential importance in catalytic processes. Geometrical parameters of the corresponding species are also described. Despite the strong interactions in dimers, the Ga···C triel bonds discussed in this study, also known as π-hole bonds, do not alter the trigonal configuration of the gallium center into tetrahedral. Electrostatic forces are the main contributors to the stabilization of these structures. Crystal structures from the Cambridge Structural Database (CSD) were analyzed to find examples of gallium centers linked to CC bonds of Lewis base units. Majority of the structures found in CSD exhibit parallel stacking-like arrangements of species containing Ga-centers. Interactions within dimers analyzed consist of several local intermolecular atom-atom interactions, primarily Ga···C links, not classified as three-centered as in typical hydrogen bonds and other interactions. DFT results were supported by the quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition analysis (EDA) approaches.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Peng Lei, Wendi Luo, Ke Deng, Bin Tu, Xunwen Xiao, Qiaojun Fang, Chen Wang, Qingdao Zeng
Summary: In this study, the abundant co-assemblies of three rigid pyridine derivatives and tetracarboxylic acid were constructed and explored using scanning tunneling microscopy and density functional theory calculations. The driving mechanisms of these assemblies were examined by studying the self-assembly of tetracarboxylic acid and co-assemblies with three different pyridine derivatives. The different intermolecular and intramolecular interactions of the co-assemblies led to the formation of diverse structures, which could be advantageous for the construction of functional nanostructures and the exploration of co-assembly mechanisms in molecular nanostructures.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chenting Yan, Rei Kinjo
Summary: The [1+2] cycloaddition reaction between a cyclic (alkyl)-(amino)aluminyl anion and diaryldiazomethane results in the formation of an AlN2 three-membered ring species, which shows interesting reactivity and properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Pavel Polestshuk
Summary: The efficient implementation of the TWOE program for evaluating atomic and interatomic energy components at post-HF level is discussed, with a systematic convergence of terms for various coupled cluster methods and comparison with CI approaches. It is found that not all components decrease in value as computational rank increases, with different patterns for atomic and interatomic energy convergence observed. The program allows for working with any ab initio method providing the two-particle density matrix, and is believed to be a useful tool for energy decomposition in real space.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Biochemistry & Molecular Biology
Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni, Stefano Zacchini, Gianluca Ciancaleoni, Fabio Marchetti
Summary: This study focused on the characterization of metal-nitrile bonding by synthesizing new nitrile compounds and related complexes, and exploring their properties using various techniques. The results revealed insights into the electron-donor power of the R substituents and the Fe-N bond energies, which were elucidated by DFT calculations on specific complexes.
Article
Chemistry, Multidisciplinary
Prasenjit Das, Pratim Kumar Chattaraj
Summary: Density functional theory (DFT) is used to explore the structure, stability, and bonding in systems with planar tetracoordinate carbon. The study reveals the stable planar form in both neutral and mono-anionic systems, with strong electron donation from ligand atoms to the carbon atom.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Tao Yang, Zhaoyang Li, Xue-Bin Wang, Gao-Lei Hou
Summary: The Dewar-Chatt-Duncanson (DCD) model is a heuristic tool to advance the development of organometallic chemistry and deepen our understanding of metal-ligand bonding. In this study, we quantified the contributions of sigma donation and pi back-donation to the metal-ligand bonding in Zeise and its family ions using state-of-the-art quantum chemical calculations. The relative importance of sigma donation and pi back-donation depends on the specific ligands and halogen atoms, and the energy levels of relevant molecular orbitals play a crucial role in controlling these contributions.
Article
Biochemistry & Molecular Biology
Maria Pilar Vazquez-Tato, Julio A. Seijas, Francisco Meijide, Santiago de Frutos, Jose Vazquez Tato
Summary: Cholic acid, a trihydroxy bile acid, exhibits a unique property where the average distance between oxygen atoms of hydroxy groups matches the tetrahedral edge distance in Ih ice. This property was utilized in the design of a cholic dimer that encapsulates a water molecule, serving as a model for studying ice-like structures. The system showed independent hydrogen bonding, supporting its use as a reference model for various systems. The calculated electron density and interaction energy validated the proposed hydrogen bonding.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Nanditha G. Nair, Krishna Prasad, Hruidya C. Babu, Mahesh Hariharan
Summary: This study explores the variations in bromine substitution for halogen synthons and identifies a novel cyclic supramolecular Br-8 synthon formed exclusively through hypervalent Br⋯Br interactions. The study also demonstrates the potential of non-electrostatic weak halogen⋯halogen contacts to generate diverse supramolecular patterns. The quantitative analysis of noncovalent interactions provides insight into the stabilizing factors of Br-8 and Br-4 synthons.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Physical
Mridula Guin, Kamal Rautela, R. A. Roopa, C. S. Shantharam, S. Begam Elavarasi
Summary: Hydrogen bonded rhodanine complexes involving oxygen, sulfur, and selenium were studied using quantum chemical calculations. The most stable structure was found to be N - H hydrogen bonded in all cases. Methyl substitution enhanced the hydrogen bond strength and demonstrated selenium's strong donor ability in the studied systems.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Aqsa Nisar, Sobia Tabassum, Khurshid Ayub, Tariq Mahmood, Hamad AlMohamadi, Asim Laeeq Khan, Muhammad Yasin, R. Nawaz, Mazhar Amjad Gilani
Summary: Density functional theory (DFT) calculations were used to evaluate the properties of supramolecular assemblies containing azobenzene and alkoxystilbazole subunits. The electronic, linear, and nonlinear optical properties of these complexes were analyzed, and the nature of inter- and intra-molecular interactions was validated. The results demonstrated that the substitution of electron-withdrawing groups on the azobenzene moiety could enhance the nonlinear optical response of the systems. The beta(0) values of the E (trans) and Z (cis) forms were compared to show the photoinduced switching mechanism.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Organic
Shanti Gopal Patra, Ruchi Jha, Himangshu Mondal, Pratim Kumar Chattaraj
Summary: The carbon atom (carbene) in Fischer and Schrock complexes exhibits electrophilic and nucleophilic properties respectively. To differentiate the reactivity patterns of these two carbenes, the philicity and multiphilic descriptor are calculated. It is found that the nucleophilic attack has higher philicity in Fischer complexes, while the electrophilic attack has higher philicity in Schrock complexes. The multiphilic descriptor is positive in Fischer and negative in Schrock, confirming the same conclusion. This understanding of reactivity parameters can help predict the catalytic application of carbene complexes without the classification of Fischer and Schrock types.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Ranita Pal, Pratim Kumar Chattaraj
Summary: This review discusses the importance of the electrophilicity index and its associated electronic structure principles in understanding the behavior of various physico-chemical systems. While these indices provide valuable insights, their predictive potential still requires further exploration.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Arpita Poddar, C. N. Ramachandran, Pratim Kumar Chattaraj
Summary: In this study, the properties of HF and its dimer inside C-60 were investigated using density functional theory. Encapsulation led to elongation of HF bond lengths and instability of (HF)(2)@C-60 for all functionals. A red shift in HF stretching frequencies was observed, indicating non-covalent interactions between HF dimer and the C-60 cage. Energy decomposition analysis showed that (HF)(2)@C-60 system was unstable except for the functional BP86-D3. QTAIM analysis confirmed the presence of a bond critical point in the hydrogen bond region of the L-shaped (HF)(2)@C-60.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Arpita Poddar, Ranita Pal, Chunying Rong, Pratim Kumar Chattaraj
Summary: This study presents the quantitative structure-property relationship (QSPR) of various chlorine substituted biphenyl systems based on linear and multi-linear regression (MLR) analysis. The lipophilicity (log K-OW) of 133 selected polychlorobiphenyl (PCB) congeners was determined using experimental log K-OW as the dependent variable and conceptual density functional theory (CDFT) and information theory (IT) based descriptors as independent variables. The relationship between experimental and predicted log K-OW was mapped using these descriptors. The best model was obtained by combining CDFT descriptor (omega) with IT quantities (S-S, S-GBP) linearly, showing a high coefficient of determination value (R-2 = 0.9261) and excellent internal predicting ability (R-CV(2) = 0.9208), indicating the importance of the mentioned descriptors for quantitative structure-property analysis of selected PCBs.
JOURNAL OF MATHEMATICAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Debdutta Chakraborty, Pratim Kumar Chattaraj
Summary: Based on Bohm-inspired quantum trajectories, the correspondence between quantum and classical phase-space dynamics in a model four-well potential is analyzed. It is found that there is a qualitative correspondence in the intermediate energy regimes, but quantum trajectories explore classically forbidden regions at both low and high energy regimes. The quantum trajectories exhibit more ergodic properties than classical ones, especially at the initial stages of the dynamics, as indicated by their Lyapunov exponents and power spectra.
THEORETICAL CHEMISTRY ACCOUNTS
(2023)
Article
Chemistry, Physical
Ruchi Jha, Pratim Kumar Chattaraj
Summary: The structure, stability, and isomerization of the Be-3(-2) system inside different-sized confinement (C-60, C-70, and C-80) were investigated using CDFT based reactivity descriptors and time dynamics simulation. The study reveals that the linear Be-3(-2) system tends to transform into the more stable cyclic Be-3(-2) structure, but this tendency is lost inside confined environments. Although the linear structure becomes bent inside confinement, the complete D-3h structure cannot be achieved.
CHEMICAL PHYSICS LETTERS
(2023)
Review
Energy & Fuels
Sukanta Mondal, Pratim Kumar Chattaraj
Summary: This article is a review that focuses on the coexistence of aromaticity and hydrogen storage potential in certain atomic clusters. It also discusses the possible role of partial charges and frail van der Waals interactions in hydrogen trapping. Our research group's contribution to this particular topic is also addressed.
Article
Chemistry, Physical
Jesus Sanchez-Marquez, Himangshu Mondal, Shanti Gopal Patra, Alejandro Morales-Bayuelo, Pratim Kumar Chattaraj
Summary: Chelotropic reactions are analyzed in this work, dividing the reaction path into reactants to transition state and transition state to products. Global reactivity descriptors based on conceptual-density functional theory (DFT) have been calculated to analyze the correlations between global and local parameters, and the aromatic nature of the transition states has been determined using NICS and GIMIC analysis.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sukanta Mondal, Gourhari Jana, Hemant K. Srivastava, Garikapati N. Sastry, Pratim Kumar Chattaraj
Summary: This study explores the ability of clathrate hydrates to encapsulate gaseous molecules. The encapsulation ability depends on factors such as cavity size, guest gaseous species, temperature, and pressure. The structure, stability, and interaction nature of dissimilar guest occupied sH hydrate cavity are investigated, considering diatomic gas molecules and small polyatomic hydrocarbons as guests. Different hybrid DFT functionals (B3LYP, M05-2X, M06) and dispersion correction (PBE0-D3) are used to calculate the thermodynamic parameters for guest molecules encapsulation. The non-covalent interaction (NCI) indices and energy decomposition analysis (EDA) are employed to understand the nature of interaction between host-guest and guest-guest systems.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Review
Chemistry, Physical
Manas Ghara, Himangshu Mondal, Ranita Pal, Pratim Kumar Chattaraj
Summary: The outstanding catalytic capability of Frustrated Lewis Pair (FLP) catalysts in activating small molecules has gained significant attention. The reactivity of FLP has been extended to the hydrogenation of various unsaturated species, and it has also been successfully applied in heterogeneous catalysis. This review article provides a brief survey of studies on FLP, including quantum chemical studies on the activation of H-2, the role of aromaticity and boron-ligand cooperation in FLP reactivity, and the cooperative action of FLP in activating other small molecules. It also discusses the hydrogenation of unsaturated species and the latest theoretical advancements in the application of FLP in heterogeneous catalysis.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Ranita Pal, Prasenjit Das, Pratim Kumar Chattaraj
Summary: Tackling the problem of global optimization is important in the fields of physics and chemistry. Soft computing techniques have made this process easier by reducing nonlinearity and instability. This Perspective discusses the mathematical models and applications of efficient soft computing techniques in computational chemistry for finding the global minimum energy structures of chemical systems. The authors present examples of global optimizations of various chemical systems using CNN, PSO, FA, ABC, BO, and hybrid techniques.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Ruchi Jha, Pratim Kumar Chattaraj
Summary: Mechanochemical synthesis has become popular due to its eco-friendly nature. The reactivity of chemical systems can be altered by applying mechanical force and changing the surrounding environment. The study focuses on the effect of confinement and mechanical stretching force on diatomic systems, such as F-2, H-2, O-2, N-2, ClBr, NaCl, CO, LiF, and HCl, using fullerene cage C-60 as confinement. The bond strength of the diatomic systems varies, with some systems showing an increase in bond strength under confinement while others show a decrease. The analysis of Natural Bond Orbital (NBO), Atoms in Molecules (AIM), and Energy Decomposition Analysis (EDA) provides insights into the reasons behind such variations.
Review
Biochemistry & Molecular Biology
Ranita Pal, Pratim Kumar Chattaraj
Summary: This article discusses the bonding between noble gases and noble metals from a quantum chemical perspective. Despite their low reactivity, noble gases can form weak bonds with noble metals such as copper, gold, and silver. Factors such as electronic structure and geometric configuration contribute to this unusual bonding behavior. The study also analyzes the energetics of possible dissociation and internal isomerization channels, as well as the nature of the bond between noble gases and noble metals.
Article
Chemistry, Physical
Ranita Pal, Gourhari Jana, Pratim Kumar Chattaraj
Summary: A strategy of handling the thermochemical stability of XOPO(OH)(2) compounds (X = F, Cl, Br) is performed by inserting noble gas (Ng) atoms (Ng = Kr, Xe, Rn) within the X-O bond. Theoretical prediction of the new compounds XNgOPO(OH)(2) and their thermochemical stability are investigated using ab initio and density-functional theory techniques. The results show that the release of Ng atom from the compounds is thermodynamically favorable but has high activation energy barriers, protecting them from dissociation at room temperature.
THEORETICAL CHEMISTRY ACCOUNTS
(2023)
Article
Biochemistry & Molecular Biology
Navya Arepalli, Sukanta Mondal, Debdutta Chakraborty, Pratim Kumar Chattaraj
Summary: This study investigates the effect of oriented electric fields (OEF) on the kinetics of Suzuki-Miyaura and metal-cluster mediated reactions through density functional theory-based calculations. The results demonstrate that OEF can enhance the reaction kinetics when applied in the appropriate direction but opposite effect occurs when the direction is flipped. OEF helps polarize transition states in the desired direction, facilitating favorable bonding interactions. Considering the need for discovering suitable catalysts, OEF can prove to be a vital route for catalyst optimization.
Article
Chemistry, Multidisciplinary
Michal Novotny, Matus Dubecky, Frantisek Karlicky
Summary: This paper investigates the accuracy of different DFT-based computational approaches in calculating the equilibrium lattice constants and exfoliation energy of hexagonal boron nitride (h-BN). The results are compared with experiments and reference QMC calculations to evaluate the accuracy of these computational methods.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2024)
Article
Chemistry, Multidisciplinary
Luigi Crisci, Federico Coppola, Alessio Petrone, Nadia Rega
Summary: The charge transfer dynamics in asymmetrically substituted indenotetracene molecules upon photo-excitation were investigated using real-time time-dependent density functional theory simulations. The study found that the electron-donating character of the substituents affects the overall electronic energy spacing and ultrafast charge transfer dynamics.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2024)
Article
Chemistry, Multidisciplinary
Vasilii Korotenko, Hendrik Zipse
Summary: The stability of various radicals and molecules has been studied using different theoretical methods, and good correlations between theoretical calculations and experimental results have been found. The effects of hydrogen bonding interactions on the stability of oxygen-centered radicals have also been investigated.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2024)
Article
Chemistry, Multidisciplinary
Oleg Egorov, Michael Rey, Dominika Viglaska, Andrei V. Nikitin
Summary: In this work, the rovibrational energy levels of four isotopologues of methylene were calculated using a new accurate ab initio potential energy surface. The accuracy of the calculations was improved by considering scalar relativistic effects, DBOC, and high-order electronic correlations. For the first time, all available experimental rovibrational transitions were reproduced with high accuracy, without any empirical corrections.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2024)