Article
Chemistry, Multidisciplinary
Guilherme Cariello, Lucas A. Zeoly, Bruno A. Piscelli, Thomas Lectka, Rodrigo A. Cormanich
Summary: Theoretical decomposition of through space spin-spin coupling constants in organofluorine compounds suggests that intramolecular hydrogen bonds are not the primary mechanism for SSCC transmission. Increasing solvent polarity may disrupt hydrogen bonds, but not necessarily the JFH SSCC. Additionally, substituent effects can greatly alter the SSCC transmission pathway. Accurate SSCC analysis requires benchmarking theoretical calculations with experimental data interpretation.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Cam-Tu Phan Dang, Nguyen Tien Trung
Summary: This study investigates the significant change in bonding characteristics of CO2 complexes induced by halogen substitution, transitioning from C···O tetrel bonds to O-H···O hydrogen bonds. The behavior and bonding nature of noncovalent interactions are thoroughly analyzed and discussed, providing insights into the effect of halogen substituents on the bonding characteristics of these interactions.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Cam-Tu Phan Dang, Nguyen Minh Tam, Thanh-Nam Huynh, Nguyen Tien Trung
Summary: In this study, the noncovalent interactions of tetrel, pnicogen, chalcogen, and halogen bonds were systematically investigated by modeling the interactions between NH3 and SiF4, PF3, SF2, and ClF. The characteristics of these interactions were examined through stability, vibrational spectroscopy, electron density, and natural orbital analyses.
Article
Physics, Condensed Matter
Alexander Platonenko, Fabien Pascale, Khaled E. El-Kelany, Francesco Silvio Gentile, Roberto Dovesi
Summary: This study discusses the impact of the charge of a point defect on the infrared spectrum and hyperfine coupling constants, using the VO defect in silicon as a reference. The calculations show that the charge state of the defect significantly affects the dominant peak position and intensity in the infrared spectrum, as well as the hyperfine constants.
PHYSICA B-CONDENSED MATTER
(2022)
Article
Chemistry, Physical
Scott A. Southern, Tamali Nag, Vijith Kumar, Michael Triglav, Kirill Levin, David L. Bryce
Summary: Experimental and theoretical studies show that tin atoms can form strong tetrel bonds when acting as tetrel bond donors, leading to significant effects on NMR parameters. The experimental trends in J couplings for tetrel bonds are similar to those for hydrogen bond donors, but NMR parameters are less suitable for measuring tetrel bond strengths.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Xin Wang, Qingzhong Li, Steve Scheiner
Summary: The structures of dimers and trimers formed by imidazole and F2TO were studied through ab initio calculations. The introduction of cooperativity from hydrogen bonding can lead to the formation of long noncovalent bonds or short covalent bonds between imidazole and F2CO, representing comparable energy minima.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Kendall D. Hughey, Minseong Lee, Jisoo Nam, Amanda J. Clune, Kenneth R. O'Neal, Wei Tian, Randy S. Fishman, Mykhaylo Ozerov, JunHee Lee, Vivien S. Zapf, Janice L. Musfeldt
Summary: In this study, high field polarization, magneto-infrared spectroscopy, and lattice dynamics calculations were used to investigate the properties of (NH4)(2)[FeCl5 center dot(H2O)] - a type II molecular multiferroic. The results showed that the electric polarization is sensitive to the field-induced spin reorientations, and the magnetoelectric coupling occurs through an orbital hybridization mechanism. Magneto-infrared spectroscopy revealed that all vibrational modes below 600 cm(-1) are sensitive to the field-induced transition to the fully saturated magnetic state. Additionally, subtle symmetry breaking of the counterions was observed across the ferroelectric transition.
INORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
N. El-Kork, A. AlMasri Alwan, N. Abu El Kher, J. Assaf, T. Ayari, E. Alhseinat, M. Korek
Summary: This study presents a theoretical investigation on the feasibility of laser cooling of LuF molecules in the fine structure approximation. Ab-initio calculations were performed to determine the potential energy curves, spectroscopic parameters, and internuclear distances of various electronic states. The results indicate that LuF is a suitable candidate for direct laser cooling, considering its electronic states and transitions. Comprehensive analyses, including Franck-Condon factors, radiative lifetimes, total branching ratio, slowing distance, and laser cooling scheme, further confirm the suitability of LuF for Doppler laser cooling.
SCIENTIFIC REPORTS
(2023)
Article
Chemistry, Multidisciplinary
Jake Williams, Eric Jonas
Summary: This study presents a novel machine learning technique that combines uncertainty-aware deep learning with rapid estimates of conformational geometries to accurately simulate solution NMR spectra. The method improves the accuracy of chemical shift values and can predict all scalar coupling values. The uncertainty quantification results show a strong correlation with accuracy and the method is able to handle stereoisomerism and disagreement regularization.
Article
Spectroscopy
Hao Wang, Junhua Chen, Wanying Cheng, Yang Zheng, Siyu Zou, Weiping Du, Xuefang Xu, Qian Gou
Summary: The rotational spectrum of the 1:1 anisole-CO2 complex was studied using a pulsed jet Fourier transform microwave spectrometer and quantum chemical calculations. Experimental observations and theoretical estimations at the B3LYP-D3(BJ)/6-311++G(d, p) level of theory suggested the presence of a dominant C center dot center dot center dot O tetrel bond and two C-H center dot center dot center dot O-CO2 weak hydrogen bonds in the complex. Johnson's non-covalent interaction, quantum theory of atoms in molecules, and natural bond orbital analyses were employed to understand the nature of non-covalent interactions in the anisole-CO2 complex.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2022)
Article
Chemistry, Physical
Yang Zheng, Sven Herbers, Qian Gou, Walther Caminati, Jens-Uwe Grabow
Summary: Besides its typical halogen donor behavior, CF3Cl is shown to reveal a new interaction site with CO2, forming a C-dot-dot-dot-Cl tetrel bond through the Cl equatorial belt. Additionally, a secondary C-dot-dot-dot-O tetrel bond and a F-dot-dot-dot-O halogen bond may also contribute to the relative orientation of the moieties in the complex.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Biochemistry & Molecular Biology
Pradeep R. Varadwaj, Arpita Varadwaj, Helder M. Marques, Koichi Yamashita
Summary: The structural stability of organic-inorganic hybrid perovskite semiconductors is determined by non-covalent interactions between the organic cations and inorganic anions. This study investigates the nature of these interactions using ion pair models and density functional theory simulations. The results reveal the importance of hydrogen and pnictogen bonds in stabilizing the ion pairs, as well as the role of tetrel bonding interactions in holding the inorganic anionic moieties together.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Ponnadurai Ramasami, Thomas A. Ford
Summary: The binary complexes formed between electron donors (ammonia, water, hydrogen fluoride, phosphine, hydrogen sulphide, and hydrogen chloride) and electron acceptors (methane and tetra-fluoromethane) were studied using ab initio molecular orbital theory. The properties investigated include molecular structures, interaction energies, vibrational spectra, and the formation of complexes through the interactions between molecular orbitals. The complexes were found to belong to various structural types depending on the combination of donor and acceptor, such as tetrel-bonded, hydrogen-bonded, halogen-bonded, pnicogen-bonded, and chalcogen-bonded. Regardless of the interaction type, the complexes were uniformly weakly bound. These results were explained in terms of donor properties and compared with previous studies on fluorine-substituted molecules.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Wanying Cheng, Yang Zheng, Sven Herbers, Huaili Zheng, Qian Gou
Summary: The rotational spectrum of 2-methoxypyridine...CO2 reveals the presence of two stable isomers stabilized by various weak interactions, with a relative population ratio of approximately 2.5. The study emphasizes the importance of multiple interactions in CO2 adsorbents, as opposed to few but strong interactions for enhanced performance. Discussions on non-covalent interactions within isomers are based on Bader's quantum theory of atoms in molecules and Johnson's non-covalent interaction analyses.
Article
Biochemical Research Methods
Mohammadmehdi Moradkhani, Ali Naghipour, Yunes Abbasi Tyula, Shahryar Abbasi
Summary: The competition between hydrogen, halogen, and tetrel bonds in the interaction between COCl2 and HOX was investigated using quantum chemistry simulations. Five configurations of adducts were optimized and spectroscopic, geometry, and energy properties were analyzed. The stability of adduct I complexes and adduct V halogen bonded complexes were found to be higher than others, which is consistent with their NBO and AIM results. The interaction energy of XB complexes depended on the nature of Lewis acid and base.
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
(2023)
Review
Chemistry, Organic
Jose Elguero, Ibon Alkorta
Summary: This mini review focuses on the relationships between hydrocarbons and carbon allotropes with regular solids and surfaces. It introduces Platonic and Archimedean solids and surfaces related to carbon allotropes, and provides an overview of how Stone-Wales defects result in a series of structures. The compound tetraoctite and its relation to the Mills-Nixon effect on cyclooctatetraene (COT) are discussed in detail.
MINI-REVIEWS IN ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Manuel Yanez, Filiberto Ortiz-Chi, Gabriel Merino, Ibon Alkorta
Summary: The interaction between ammonia and Be-n clusters (n < 1-10) was investigated using density functional theory and ab initio calculations. The results show that regardless of the cluster size, the ammonia structure and the Be cluster structure are not preserved due to the dissociation of N-H bonds and the migration of hydrogen atoms towards available Be atoms. This migration leads to the formation of stable Be-H bonds and enhances the strength of Be-N bonds. The most stable complex is formed with the beryllium trimer, which contains three N-Be and three Be-H bonds.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
M. Merced Montero-Campillo, Ibon Alkorta, Otilia Mo, Jose Elguero, Manuel Yanez
Summary: The structures, bonding, and stability of (MF2)(m):(M ' F-3)(n) (M = Be, Mg; M ' = B, Al; m = 0,1,2; n = 0,1,2) clusters were studied. Replacing first-row elements with second-row elements led to changes in bonding enthalpies and the formation of more stable structures in trimers and tetramers. The electronic environment around each monomer did not significantly change with the nature of the monomers or the size of the cluster. It was found that the stability of larger clusters can be predicted based on the values obtained for smaller ones.
Article
Chemistry, Physical
Paul L. A. Popelier, Ibon Alkorta
Summary: The aim of this study is to experimentally connect the interatomic exchange-correlation energy with the energy decomposition method IQA. The nuclear magnetic resonance (NMR) J-coupling constant 3J(H,H ') is identified as a suitable experimental quantity due to its strong correlation with QTAIM's delocalization index (DI). By investigating the correlations between 3J(H,H ') and a relevant dihedral angle in several compounds, it is concluded that the inter-hydrogen exchange-correlation energy Vxc(H,H ') shows the best agreement with experiment, especially when multiplied with the internuclear distance RHH '.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Editorial Material
Chemistry, Physical
Ibon Alkorta, John M. C. Plane, Jose Elguero, Juan Z. Davalos, A. Ulises Acuna, Alfonso Saiz-Lopez
Summary: In this study, the authors address the argument raised in a previous comment regarding the energy of the NO3 radical and its impact on the reaction profiles of the NO3 radical with various compounds. They used 49 DFT functionals to obtain the optimized geometry of the NO3 radical and compared the results from different functionals. The thermodynamic values of three reactions were calculated using the functionals with smaller errors and compared with experimental data. The authors also recalculated the barriers of the reactions using these functionals and observed a difference of 10.5 kJ mol(-1) compared to the results obtained with the M08HX functional.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Ibon Alkorta, Anthony Legon
Summary: The reduced nucleophilicities of axially symmetric molecules B were determined using the equation D-e/sigma(min) = N-B/sigma(min)) E-XY = (sic)E-XY. Graphs of D-e/sigma(min) versus E-XY for different groups of B showed straight lines through the origin, indicating a common (reduced) nucleophilicity for each group.
Article
Chemistry, Physical
Marta Delgado Gomez, Marco Marazzi, Jose Elguero, Maxime Ferrer, Ibon Alkorta
Summary: Theoretical chemistry was used to design a system based on ammonia boranes catalyzed by pyrazoles for the production of dihydrogen as clean fuel. The reactivity of ammonia borane and cyclotriborazane with different pyrazole catalysts was investigated. The results suggest a catalytic cycle in which ammonia borane can store and produce dihydrogen and amino borane, and amino borane can trimerize to produce cyclotriborazane that can also generate dihydrogen. This study proposes a progress in using environmentally sustainable (metal free) catalysts to efficiently extract dihydrogen from small B-N bonded molecules.
Article
Engineering, Chemical
Eduardo J. Cueto-Diaz, Alberto Castro Muniz, Fabian Suarez Garcia, Ibon Alkorta, Maria Pilar Valles Gonzalez, Eva Mateo-Marti
Summary: Carbon dioxide solid sorbents produced from mesoporous functionalized silica microparticles (SBA-15) were theoretically studied using density functional theory and empirically evaluated for their CO2 adsorption capacity. Different types of organosilyl groups were tested, and SBA-15 bearing (3-aminopropyl)triethoxysilane (APTES) showed significant enhancement in CO2 adsorption compared to pristine SBA-15. The maximum adsorption capacity under conditions relevant to CO2 capture was increased from 0.34 mmol/g (SBA-15) to 1.15 mmol/g (SBA-15@NH2).
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Physical
Ibon Alkorta, Anthony Legon
Summary: The strength of binding in hydrogen-bonded complex B & BULL;& BULL;& BULL;HX can be determined by measuring the equilibrium dissociation energy D(e) and through properties of components B and HX. By comparing calculated D(e) values with those obtained from the proposed equation, it is shown that the equation leads to accurate results in general.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Multidisciplinary Sciences
Maxime Ferrer, Ibon Alkorta, Jose Elguero, Josep M. Oliva-Enrich
Summary: The reactivity of B3P3-doped hexa-cata-hexabenzocoronene (B3P3-NG) towards carbon dioxide was studied. It was found that the compound can capture multiple CO2 molecules due to its poly-cyclic Frustrated Lewis Pair system.
SCIENTIFIC REPORTS
(2023)
Article
Chemistry, Multidisciplinary
Ibon Alkorta, Jose Elguero
Summary: This work theoretically examines the migration of borane groups between nitrogen atoms of pyrazolyl rings. BH2 pyrazol-1-yl derivatives were used as a model to study the effects of substituents on the pyrazole ring. The interacting quantum atoms methodology was employed to analyze the energy partitioning and mutual interaction between pyrazole and BH2 group.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Carlos Martin-Fernandez, Maxime Ferrer, Ibon Alkorta, M. Merced Montero-Campillo, Jose Elguero, Marcos Mandado
Summary: Multiply charged complexes bound by noncovalent interactions have been studied in organic and main group inorganic systems. In this work, we investigate similar complexes in organometallic systems containing transition metals and provide insights into their existence. Our results reveal that carboxylic acid-containing dimers are more strongly bonded and have higher barriers to dissociation compared to amide ones, and cationic complexes are more stable than anionic ones. Additionally, we report a symmetric proton transfer in the metastable phase.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Maxime Ferrer, Ibon Alkorta, Jose Elguero, Josep M. Oliva-Enrich
Summary: A theoretical study was conducted to investigate the reaction between several borataacenes and CO2. The study explored the influence of a counterion, cation complexation, and solvent effects. The computational results successfully predicted the observed syn/anti selectivity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Biochemistry & Molecular Biology
Otilia Mo, M. Merced Montero-Campillo, Manuel Yanez, Ibon Alkorta, Jose Elguero
Summary: In this study, the common bonding patterns in pure and mixed clusters of beryllium and magnesium derivatives were explored using chemical bonding tools. The results showed interesting differences in stability sequences between hydrides and fluorides/chlorides in dimers. Additionally, trimers exhibited peculiarities associated with compact trigonal cyclic structures competing in stability with more conventional hexagonal and linear forms. This study provides insights into previously unexplored structures.
Article
Chemistry, Physical
Ibon Alkorta, Anthony Legon
Summary: In this study, the nucleophilicities of methane, ethane, cyclopropane, ethyne, and ethene acting as Lewis bases were determined through experimental and computational methods. The inductive effect of the methyl group when ethyne is methylated was also investigated.
CHEMICAL PHYSICS LETTERS
(2023)