Article
Chemistry, Multidisciplinary
Petra Stanic, Ivana Niksic-Franjic, Kresimir Molcanov
Summary: The pancake bonding in dimers of semiquinoid radical cations in a novel compound, TMPD chloride co-crystal with 2,5-dichlorohydroquinone, was investigated using X-ray charge density and quantum chemical computations. The pancake-bonded dimer consists of parallel rings with a transversal offset, with an interplanar separation distance of 3.1191(1) angstrom and a centroid distance of 3.2022(2) angstrom. AIM analysis revealed four symmetry-independent bonding critical points and a cage critical point between the TMPD cations in the dimer, with a maximum electron density of 0.055 e angstrom-3. The highest occupied molecular orbital extends between both rings of the dimer. The estimated energy of the covalent component is -3.24 kcal mol-1.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Haruka Abe, Ayumi Kawasaki, Takashi Takeda, Norihisa Hoshino, Wakana Matsuda, Shu Seki, Tomoyuki Akutagawa
Summary: The dianionic bis(propionate)-naphthalenediimide can form cation-anion salts with various metal ions, of which Na+ and K+ salts exhibit high ionic conductivities and flexible lattice modulation, while Rb+ and Cs+ salts show relatively rigid lattice structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Xiaoyan Ji, Chongyang Zhao, Jing Xie
Summary: This study investigates a recently discovered S(N)2 reaction mechanism, the front-side complex (FSC) or halogen-bonded complex (XC) mechanism, which combines the traditional front-side attack and back-side attack Walden-inversion mechanisms. The XC pathway has a deeper well depth compared to the back-side attack for certain nucleophiles. The barriers of FSA and BSA paths increase with solvation, while the change in XTS depends on the nucleophile type.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Jakob Heller, Ethan M. Cunningham, Christian van der Linde, Milan Oncak, Martin K. Beyer
Summary: Controlled activation of water molecules is crucial for efficient water splitting, as shown by studying the insertion reaction of hydrated singly charged manganese ions using IRMPD and mass spectrometry techniques. Comparison of IRMPD spectra and quantum chemical calculations reveal that the inserted structure requires stabilization through hydration.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Yu-Han Lu, Zhuo-Tao Zhang, Hong-Yu Wu, Min -Hang Zhou, Hai-Yang Song, Hong -Tao Ji, Jun Jiang, Jin-Yang Chen, Wei -Min He
Summary: The first example of TBAI/H2O cooperative electrocatalytic coupling-annulation of quinoxalin-2(1H)-ones with N-arylglycines was developed. A broad range of tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones were obtained in good to excellent yields with exclusive chemoselectivities and excellent regioselectivities. The H-hydrogen bond served as a key factor for the electrocatalytic production of aminomethyl radical at lower oxidative potential.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Physical
Sayoni Mitra, Nan Yang, Laura M. McCaslin, R. Benny Gerber, Mark A. Johnson
Summary: The study shows that nitric acid undergoes charge separation in a water medium and forms specific structures in the presence of ten water molecules, providing important information for further understanding of charge separation.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Manohar Shivaji Padmor, Palak Vishwakarma, Srinu Tothadi, Sanjay Pratihar
Summary: In this study, a flexible multidentate ligand was used as a reusable catalyst for C-/N-alkylation of alcohols, exhibiting higher reaction efficiency and selectivity compared to individual components. The ligand brings rigidity and self-assembling to ordered crystalline supramolecular materials through its flexible binding sites, diverse hydrogen bond donor-acceptor fragments, rigidity, variable coordination mode, and cooperativity, thereby avoiding coordinatively saturated active sites and providing higher reaction efficiency and selectivity.
Article
Polymer Science
Jiarui Wang, Chao Wang, Fan Zhang, Xinyue Wang, Hao Zhang, Ying Liu, Xiaona Huang, Hang Jiang, Hui Chi, Yungang Bai, Kun Xu, Pixin Wang
Summary: The use of pure water as the reaction medium for the dispersion polymerization of N-vinyl formamide and acrylonitrile can overcome the drawbacks of high molecular weight loss, environmental pollution, and high cost. The dispersion polymer products have great fluidity and help to improve the charge density of polyamidine. Compared to solution polymerization, the copolymer products of dispersion polymerization exhibit higher amidinization rate, charge density, and flocculation performance.
JOURNAL OF POLYMER RESEARCH
(2023)
Article
Multidisciplinary Sciences
Chihiro Ikeda, Kazuo Taku, Tsumugi Miyazaki, Rikako Shirai, Richard S. Nelson, Hiroshi Nyunoya, Yasuhiko Matsushita, Nobumitsu Sasaki
Summary: Our study reveals that the expression of the tobacco virus resistance gene N can be enhanced by the presence of introns, particularly intron 1. Both introns 1 and 2 are important for not only enhanced gene expression, but also for induction of cell death and local resistance to virus spread in Nicotiana benthamiana.
SCIENTIFIC REPORTS
(2021)
Article
Chemistry, Multidisciplinary
Soumen Singha, Bhaskar Khanra, Somen Goswami, Rituparna Mondal, Rajkumar Jana, Arka Dey, Sanjoy Kumar Dey, Partha Pratim Ray, Corrado Rizzoli, Rajat Saha, Sanjay Kumar
Summary: The study presents a [Mg(H2O)(6)](2+) templated supramolecular framework with unique properties, including crystal structure, supramolecular structure, band structure, and various properties such as conductivity, semiconductor behavior, dielectric behavior, and photoresponsiveness. The complex demonstrates good proton conductivity, semiconductor characteristics, and anomalous dielectric behavior under vacuum conditions, as well as the ability to absorb electromagnetic radiation and exhibit enhanced conductivity under visible light. The ITO/complex/Al sandwiched device shows Schottky barrier diode-like behavior, with a rectification ratio that increases significantly under visible light, indicating the complex's potential application in optoelectronic devices.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Ayumi Kawasaki, Takashi Takeda, Norihisa Hoshino, Wakana Matsuda, Shu Seki, Tomoyuki Akutagawa
Summary: The study investigates the impact of different alkyl chain lengths on the phase transition behavior, molecular assembly structure, dielectric response, and transient conductivity of Cn-BSNDI salts, revealing that short-chain salts have static structures, medium-chain salts exhibit large dielectric responses, and long-chain salts are primarily influenced by thermal fluctuations of the long alkyl chains.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Inorganic & Nuclear
Monica Soler, Preet Mahalay, Wolfgang Wernsdorfer, Daphne Lubert-Perquel, John C. Huffman, Khalil A. Abboud, Stephen Hill, George Christou
Summary: The family of reduced single-molecule magnets [Mn12O12(O2CR)(16)(H2O)(4)](n) (n = 1, 2) has been expanded by synthesizing new members using I as a stoichiometric one-electron reducing agent. The study includes electrochemical data, NMR spectra, and crystal structures of two complexes, revealing interesting properties and behaviors of these nanomagnets.
Article
Spectroscopy
Li Wang, Yan-Li Liu, Di He, Sheng-Hui Chen, Quan-Jiang Li, Yan-Liang Zhao, Mei-Shan Wang
Summary: In this study, the effects of ring size on the optical properties of necklace-type molecules were investigated. The results showed that increasing the size of the CPP ring was an effective way to enhance the nonlinear optical properties of these compounds, which is important for improving their optical performance.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Chemistry, Physical
Sean A. C. McDowell
Summary: A computational study was conducted to investigate the relative stabilities of mono-deuterated isotopomers of three sets of binary hydrogen-bonded complexes. The results showed that deuterium-bonded isotopomers are energetically preferred and this preference can be explained by a simple theoretical model.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Engineering, Environmental
Xiaolin Li, Yili Wang, Shuoxun Dong, Chenyang Liu, Siying Wang, Wenfen Liu
Summary: Lanthanum composites are promising candidates for phosphorus adsorption due to their specific interactions. This study successfully achieved ideal lanthanum hydrolysis-induced assembly in a cellulose hydrogel network, resulting in improved dispersion of La(OH)3 clusters. The composite CCH@La exhibited high adsorption capacity, wide applicability, and good selectivity.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Physical
Carlos Mejuto-Zaera, Demeter Tzeli, David Williams-Young, Norm M. Tubman, Mikulas Matousek, Jiri Brabec, Libor Veis, Sotiris S. Xantheas, Wibe A. de Jong
Summary: Iron-sulfur clusters are important functional motifs in biological catalytic centers, capable of performing important chemical transformations at ambient conditions. The electronic structure of these clusters is complex and sensitive to geometric changes, requiring large active space calculations to reveal their properties.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Naoya Takeda, Keisuke Hirata, Kazuya Tsuruta, Garrett D. Santis, Sotiris S. Xantheas, Shun-ichi Ishiuchi, Masaaki Fujii
Summary: The gas phase protonated nicotine exhibits two protomers, pyridine and pyrrolidine, with varying relative populations depending on the thermalizing trap temperature. The combination of IR spectroscopy and electronic structure calculations reveals a small energy difference between the two protomers, and one of the pyrrolidine protomers closely resembles the X-ray structure of nicotine in the nicotinic acetylcholine receptor (nAChR).
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Demeter Tzeli, Sotiris S. Xantheas
Summary: We present a new implementation using Many-Body Expansion (MBE) to explain the breaking of covalent bonds, extending its applications to molecules. The analysis shows that the 2-B term is the largest in MBE with higher order terms decreasing in size. Additionally, an alternative explanation for the anomaly in bond energies between atoms is provided.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Kristina M. Herman, Anthony J. Stone, Sotiris S. Xantheas
Summary: We present a classical induction model to evaluate the three-body ion-water-water (I-W-W) and water-water-water (W-W-W) interactions in aqueous ionic systems. The accuracy of the classical model is benchmarked against an accurate dataset, and it demonstrates excellent agreement with the reference second order Moller-Plesset and coupled-cluster single double and perturbative triple [CCSD(T)] three-body energies.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Correction
Chemistry, Physical
Joani Mato, Demeter Tzeli, Sotiris S. S. Xantheas
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Garrett D. Santis, Naoya Takeda, Keisuke Hirata, Kazuya Tsuruta, Shun-ichi Ishiuchi, Sotiris S. Xantheas, Masaaki Fujii
Summary: A joint experimental-theoretical study was conducted to investigate the structure and infrared spectra of gas phase monohydrated nicotine and nornicotine. The protonation sites were determined based on the results. The study found that in the gas phase NICH+ & BULL;& BULL;& BULL;(H2O) complex, the protonation ratio of pyrrolidine to pyridine is 8:2, which is different from the nonhydrated gas phase NICH+ and the predominantly present pyrrolidine-NICH+ in aqueous solution. In addition, only the pyridine-NORH+ protomer was observed in nornicotine.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Kristina M. Herman, Sotiris S. Xantheas
Summary: We present a new formulation of the many-body expansion (MBE) for periodic systems and apply it to 7 ice polymorphs. The method is validated by comparing the lattice energies computed using the MBE with those obtained using periodic boundary conditions and Ewald summation. This development enables the quantification of many-body contributions to the lattice energy of ice polymorphs and provides insights into their solid-state properties.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Kristina M. Herman, Sotiris S. Xantheas
Summary: This study assesses the performance of 7 pairwise additive and 8 many-body potentials in reproducing the binding energy and many-body expansion of water clusters. It is found that pairwise additive potentials generally overestimate the binding energy, while many-body potentials can accurately reproduce the electronic binding energies. Furthermore, trends in the potentials with increasing cluster size can be identified. These results have important implications for the development of future interaction potentials.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Editorial Material
Chemistry, Physical
Thom H. Dunning Jr, Mark S. Gordon, Sotiris S. Xantheas
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
So Hirata, Yasuteru Shigeta, Sotiris S. Xantheas, Rodney J. Bartlett
Summary: This article presents a new method for studying helical polymers, which can calculate their energy, structure, and vibrational frequencies. It utilizes Gaussian spherical harmonics basis functions with frequency-dependent Dyson self-energy for infinite helical polymers. This method can handle incommensurable structures and can also predict the properties of infinitely catenated chains of nitrogen or oxygen.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Jacob M. M. Finney, Tae Hoon Choi, Rachel M. M. Huchmala, Joseph P. P. Heindel, Sotiris S. S. Xantheas, Kenneth D. D. Jordan, Anne B. B. McCoy
Summary: The energetically low-lying Zundel-Eigen isomers of the protonated water hexamer were studied using high-level ab initio calculations with zero-point corrections. A stable intermediate isomer consisting of a four-membered ring with two single acceptor water molecules was found during the Zundel-Eigen isomerization. Diffusion Monte Carlo calculations with anharmonic vibrational effects showed well-defined structures for all three isomers of H+(H2O)(6) and D+(D2O)(6). The energetic ordering of the isomers changed upon deuteration, and the implications for the vibrational spectra of H+(H2O)(6) and D+(D2O)(6) were discussed.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Multidisciplinary Sciences
Wenjin Cao, Hui Wen, Sotiris S. Xantheas, Xue-Bin Wang
Summary: In this study, direct evidence for the presence of a fourth water molecule in hydroxide's primary hydration shell is provided through a combined study using high-resolution cryogenic experimental photoelectron spectroscopy and high-level quantum chemical computations.
Article
Chemistry, Physical
Joani Mato, Soohaeng Yoo Willow, Jasper C. Werhahn, Sotiris S. Xantheas
Summary: By using Mg+ metal, we were able to extend the size range of aqueous clusters and extrapolate to the bulk limit of the solvated electron's vertical detachment energy (VDE) to a value exceeding 3,200, which is significantly larger than previous experimental or theoretical measurements. We established a relationship between the VDE and the energy difference between Mg+(H2O)(n) and Mg2+(H2O)n systems, as well as the metal's second ionization potential. The extrapolated bulk VDEs for the localized surface electron in semiempirical and ab initio calculations were found to be in excellent agreement with the experimental results.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Physics, Nuclear
Theodore Depastas, George A. Souliotis, Demeter Tzeli, Sotiris S. Xantheas
Summary: This study extends the many-body expansion (MBE) to the light nuclear systems 3H and 3He, considering the nucleonic degrees of freedom. The total energy of the 2H nucleus is calculated using the Pauli nucleonic dynamics (PND) model and is found to be in good agreement with the experimental value. The application of MBE yields results for the three-body term in the 3H nucleus comparable with previous estimates, and for the first time for the 3He nucleus.
Article
Chemistry, Physical
Kristina M. Herman, Sotiris S. Xantheas
Summary: We have introduced a new formulation of the many-body expansion (MBE) that connects gas-phase clusters to infinite solids via a hierarchical procedure. The validity of the method has been demonstrated for periodic systems by comparing computed lattice energies up to the 4-body in the MBE with those obtained using periodic boundary conditions and an Ewald summation for the 7 ice polymorphs. This development allows for the quantification of many-body contributions to the lattice energy of various ice polymorphs, which range from 7 to 24% of the total lattice energies.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)