Article
Geochemistry & Geophysics
Jordon D. Hemingway, Madison L. Goldberg, Kevin M. Sutherland, David T. Johnston
Summary: This paper highlights the importance of theoretically estimating oxygen isotope fractionation factors in various sulfate species using quantum computational chemistry, providing a foundation for interpreting experimental and observational results related to sulfur-cycle processes. The accuracy of the methodological scaling factors greatly impacts the predictions, and further research is needed to improve the estimates.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2022)
Article
Materials Science, Multidisciplinary
Zijian Zhu, Yang Li, Xiaofei Li, Huiming Qiu, Lei Fang, Lingcheng Zheng, Juan Gao, Guang Zhu
Summary: In this study, Fe, Co bimetallic doped zeolite imidazolate framework (M@CoFe-ZIF-8) was developed as a catalyst for optimizing the performance of Zn-Air batteries. The pyrolysis treatment resulted in the formation of an entangled structure of 100 nm-sized ZIF-8 particles and carbon nanotubes (CNTs). The CoFe@MNC-CNTs catalyst exhibited excellent catalytic activity and cycling stability, outperforming commercially available catalysts in terms of half-wave potential and power density.
DIAMOND AND RELATED MATERIALS
(2023)
Article
Chemistry, Physical
Minghao Hua, Xuelei Tian, Shuo Li, Anchen Shao, Xiaohang Lin
Summary: This study investigates the surface aggregation of Pt atoms on the Pt/Ag(111) surface under different conditions using density functional theory calculations and Monte Carlo simulations. The results reveal the decisive influence of CO-CO interactions and the competition between CO-metal interactions and CO-CO repulsion. Two methods for synthesizing the surface Pt atomic system are found, and the Pt distribution can be controlled by adjusting the concentration. An ordered structure with the maximized number of Pt monomers and homogeneous distribution on the surface is observed. The ordered Pt3Ag(111) surface shows a lower overpotential compared to pure Pt(111), suggesting its potential as a candidate for ORR catalysts with rich active sites and a low overpotential.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Eri Muramoto, Wei Chen, Xiwen Jia, Cynthia M. Friend, Philippe Sautet, Robert J. Madix
Summary: This study quantitatively compares the rate constant parameters for formate decomposition on Au(110) and Cu(110) using both experiment and theory, revealing higher entropy of the transition state and pre-exponential factor exceeding expected values. Reasonable agreement is obtained between experiment and theory for the pre-exponential factors, but the experimentally determined activation energies remain consistently higher than those computed by DFT.
Review
Chemistry, Multidisciplinary
Robert E. Warburton, Alexander Soudackov, Sharon Hammes-Schiffer
Summary: Proton-coupled electron transfer (PCET) is crucial in electrocatalytic processes. Various theoretical and computational methods have been developed to study electrochemical PCET and calculate related potentials and energies. Periodic density functional theory is also utilized to perform molecular dynamics simulations. Maintaining a constant electrode potential and modeling complex interactions in the electric double layer have been explored. Both homogeneous and heterogeneous electrochemical PCET have been studied, providing analytical expressions for rate constants and current densities.
Article
Astronomy & Astrophysics
Denis Duflot, Celine Toubin, Maurice Monnerville
Summary: This study investigated the adsorption of atoms and small molecules on hexagonal crystalline and amorphous ice clusters. The binding energies at different adsorption sites were explored, with most species forming physisorption with small binding energies, while carbon atoms formed unique molecules. The interaction energies obtained may help refine astrochemical models, and the methodology could be applied to other surfaces and larger adsorbates.
FRONTIERS IN ASTRONOMY AND SPACE SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Yolande Ikala Openda, Bokolombe Pitchou Ngoy, Jules Tshishimbi Muya, Tebello Nyokong
Summary: The study found that quaternized derivatives have significant inhibitory effects on the biofilms of S. aureus and E. coli, making them suitable for photodynamic antimicrobial chemotherapy with high activity in generating singlet oxygen. The small deviation observed between the calculated and experimental results primarily arises from the solvent effect.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Dong Zheng, Ying Yuan, Feng Wang
Summary: Force fields for seven small solute molecules were created using the AFM method with good agreement between predicted and experimental hydration free energies, except for 1,4-butanediol. Further investigation suggested that LMP2 may not be accurate for computing HFEs for alcohols with AFM. Other properties like enthalpy of hydration, diffusion constants, and vibrational spectra were also computed using the developed force fields.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Julianna Chedid, Nedjie Jocelyn, Henk Eshuis
Summary: The study examined the binding energies, structures, and vibrational frequencies of water clusters, revealing that the direct RPA method provides accurate structural parameters but tends to systematically underestimate binding energies and exhibit strong basis set size dependence.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Zhi-You Wei, Li-Jiang Yang, Shi-Yan Gong, Hong-Guang Xu, Xi-Ling Xu, Yi Qin Gao, Wei-Jun Zheng
Summary: The microsolvation of alkaline-earth dihalides in water was investigated to understand solvation processes, showing different trends in vertical detachment energies as cluster size increases for CaCl2, CaBr2, CaI2, and CaF2. Differences in structures and coordination numbers between the dihalides are consistent with their solubility variations in water.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Inorganic & Nuclear
Wenhao Liu, Shipeng Geng, Wenda Zhang, Fuhui Liao, Mingxue Tang, Hui Fu, Xiaojun Kuang
Summary: The study investigates the defect structures in oxide ion conductors, finding that La9.33+x(SiO4)(6)O2+1.5x apatites do not contain steady-state SiO5 in the defect structures. This new atomic-level understanding could guide the design of new solid oxide fuel cell electrolyte materials.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Eddy Lontchi, Marcos M. Mason, Monica Vasiliu, David A. Dixon
Summary: The structures of mono-, di-, and tri-bridge isomers of M2O5 and MO2 and MO3 fragments for M = V, Nb, Ta, and Pa were optimized using density functional theory. The lowest energy dimer isomer was di-bridge for M = V and Nb and tri-bridge for M = Ta and Pa. The energetics were predicted using single point CCSD(T) calculations and the Feller-Peterson-Dixon approach. The predicted bond dissociation energies and ionization energies provided insights into the chemical properties of the compounds.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Zhen-Chao Long, Zhi-You Wei, Kai-Wen Liu, Xi-Long Li, Xi-Ling Xu, Hong-Guang Xu, Wei-Jun Zheng
Summary: The structures and bonding properties of lithium polysulfide clusters LiSn-/0 (n = 3-5) and Li2S4-/0 were investigated. The vertical detachment energies of LiS3-, LiS4-, LiS5-, and Li2S4- were determined. The results provide insights into the formation of lithium polysulfides in lithium sulfur batteries.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Jianfu Chen, Menglei Jia, Jinglin Wang, Peijun Hu, Haifeng Wang
Summary: The volcano-shaped activity curve is commonly used to analyze activity trends among different catalysts, with the peak height representing the highest possible activity. This study shows that the peak height is strongly influenced by the structural features of catalyst surfaces and can be improved by reducing the intercept of the Bronsted-Evans-Polanyi (BEP) relation. Furthermore, the use of transition metal oxides (TMOs) in surpassing the activity limit of metals for molecule dissociation is discussed.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Review
Chemistry, Inorganic & Nuclear
Kizashi Yamaguchi, Mitsuo Shoji, Hiroshi Isobe, Takashi Kawakami, Koichi Miyagawa, Michihiro Suga, Fusamichi Akita, Jian-Ren Shen
Summary: This review elucidates the geometric and electronic structures of the catalytic CaMn4Ox (x = 5, 6) cluster in the water oxidation process in PSII, using high-resolution X-ray diffraction and serial femtosecond crystallography experiments, as well as theoretical computations. The interplay between experimental and theoretical methods effectively reveals the coordination structures and spin states of the cluster, and implications of these findings for artificial catalyst development are discussed.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Physical
Gabriel L. C. de Souza, Kirk A. Peterson
Summary: This study investigated the O-H bond dissociation enthalpies (BDEs) and ionization potential (IP) of gallic acid (GA) using different computational methods, with M06-2X identified as the most suitable DFT functional for studying its antioxidant potential.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Physical
Amelia Zutz, Kirk A. Peterson, David J. Nesbitt
Summary: This study presents the first quantum-state-resolved collisional energy-transfer investigations of supersonically cooled NO colliding with hot, molten Ga surfaces. Efficient rotational and spin-orbit excitation, as well as vibrational excitation of NO at the gas-molten metal interface, were observed. The results provide evidence for nonadiabatic surface hopping dynamics and significant contributions from a nonadiabatic excitation mechanism involving resonant energy transfer.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Physical
Monica Vasiliu, Kirk A. Peterson, David A. Dixon
Summary: Thermodynamic properties of chalcogens and halogens hydrides and dimers were predicted using a composite-correlated molecular orbital theory approach. The results showed that At-2 has a small bond dissociation energy and H2Po is unstable to dehydrogenation. HAt was predicted to be a stronger acid than H2SO4 in the gas phase.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Physical
Zhaoguo Zhu, Mary Marshall, Kit H. Bowen, Kirk A. Peterson
Summary: Thorium-gold negative ions ThAu2-, ThAu2O-, and ThAuOH- have been observed and characterized through experimental and theoretical calculations. Two separate isomers of ThAuOH- were found in the calculations, and both were detected in the photoelectron spectrum. Excited electronic states of the neutral molecules were reported, and atomization energies and heats of formation were calculated. Natural bond orbital analysis revealed that the sigma bonds between Th and Au consist of predominately sd hybrids on Th bonding with the Au 6s orbital. Comparisons with F-analogs showed similar behavior of Au, although Th-F sigma bonds were more ionic compared to Th-Au. The importance of this study is rated 7 out of 10.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Monica Vasiliu, Kirk A. Peterson, Mary Marshall, Zhaoguo Zhu, Burak A. Tufekci, Kit H. Bowen, David A. Dixon
Summary: High-level electronic structure calculations of ThH, ThH-, and ThH+ were performed and compared to experimental measurements. The inclusion of spin-orbit coupling was found to be critical for predicting the ground-state ordering. The results provide insights into the electron affinity, detachment energy, and photoelectron spectrum of ThH-.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Gabriel F. de Melo, Monica Vasiliu, Gaoxiang Liu, Sandra Ciborowski, Zhaoguo Zhu, Moritz Blankenhorn, Rachel Harris, Chalynette Martinez-Martinez, Maria Dipalo, Kirk A. Peterson, Kit H. Bowen, David A. Dixon
Summary: The properties of the anion UN-, including its electronic structure and bond dissociation energy, were investigated through high-level calculations. The results matched well with experimental measurements and provided valuable insights into the stability and structure of UN-. The study also revealed differences in bond dissociation energy between UN- and its neutral and cation counterparts.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Rachel M. Harris, Zhaoguo Zhu, Deepika, Burak A. Tufekci, Kirk Peterson, Puru Jena, Kit H. Bowen
Summary: Anion photoelectron spectroscopy and first-principles quantum chemistry are used to demonstrate the substitution of F in UF6 with Au. UAu6 exhibits strong Au-Au interactions, leading to three low-lying isomers. All the UAu6 isomers have open-shell electrons localized on the central U atom. The measured adiabatic electron affinity and vertical detachment energy are in good agreement with calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yury Minenkov, Luigi Cavallo, Kirk A. Peterson
Summary: The impact of complete basis set extrapolation schemes, diffuse functions, and tight weighted core functions on predicted enthalpies of formation via the DLPNO-CCSD(T1) approach has been investigated for neutral H,C,O-compounds. The results show that all tested extrapolation schemes have a mean unsigned deviation below 2 kJ mol(-1) relative to the experiment. The influence of tight weighted core functions on atomization energies is small, and core-valence correlation effects converge at triple-zeta level. The effect of diffuse function augmentation converges slowly and cannot be reproduced accurately with double-zeta or triple-zeta calculations.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
David H. Bross, George B. Bacskay, Kirk A. Peterson, Branko Ruscic
Summary: The thermochemistry of halocarbon species containing iodine and bromine is examined through an extensive interplay between new FPD style composite methods and a detailed analysis of all available experimental and theoretical determinations using the thermochemical network that underlies the ATcT. The study found that the convergence of composite thermochemistry methods is slower for halocarbon species containing iodine and bromine, leading to higher computational expense. Spin-orbit coupling was identified as a critical component, especially for iodine containing molecular species. This study provides accurate and reliable heats of formation for 38 halogen containing systems.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Gabriel F. de Melo, Monica Vasiliu, Gaoxiang Liu, Sandra Ciborowski, Zhaoguo Zhu, Moritz Blankenhorn, Rachel Harris, Chalynette Martinez-Martinez, Maria Dipalo, Kirk A. . Peterson, Kit H. Bowen, David A. . Dixon
Summary: A combination of theoretical calculations and experimental measurements is used to study the properties of UC, UC-, and UC+ molecules, and the results are consistent with the experimental observations.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Wenjing Zhang, Ashley R. E. Hunt, Jung Soo Kim, Maria Demireva, Kirk A. Peterson, P. B. Armentrout
Summary: Guided ion beam tandem mass spectrometry was used to study the reactions of U+ with O-2 and CO. The formation of UO+ in the U+ + O-2 reaction is barrierless and exothermic, with a reaction efficiency that increases with higher collision energies. Both the formation of UO+ and UC+ in the U+ + CO reaction are endothermic. Analysis of the kinetic energy dependent cross sections reveals 0 K bond dissociation energies of D-0(U+-O)=7.88 +/- 0.09 eV and D-0(U+-C)=4.03 +/- 0.13 eV, which are consistent with previous experimental values. Quantum chemical calculations were also performed to explore the electronic states of UO+ and UC+ and the potential energy surfaces for the reactions, yielding further insights into the reaction mechanisms. The experimental bond dissociation energies are found to be similar to those of transition metal congeners.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Rachel M. M. Harris, Zhaoguo Zhu, Burak A. A. Tufekci, Purusottam Jena, Kirk A. A. Peterson, Kit H. H. Bowen
Summary: This study presents a collaborative effort between experimental and theoretical approaches to elucidate the electronic and molecular structures of uranium-gold clusters. Anion photoelectron spectra of UAu n (-)(n = 3-7) were measured using different laser and photon energies, and first-principles calculations were performed to determine the geometry and electronic structure of each cluster. The results showed that smaller clusters resemble UF n species, but deviations start to appear starting with UAu5 due to the competition between U-Au and Au-Au bonding.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Devon M. Andriola, Kirk A. Peterson
Summary: The atomization enthalpies of U(VI) species UF6 and uranium oxyhalides UO2X2 (X = F, Cl, Br, I, and At) were calculated using a relativistic Feller-Peterson-Dixon approach. The calculations were in good agreement with experimental values for UF6 and UO2F2, while the uncertainty in the experimental values may affect the accuracy of the results.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Gabriel L. C. de Souza, Kirk A. Peterson
Summary: This work presents an investigation on the ionization potentials of the glycine molecule and provides accurate IPs for different conformations of glycine. The findings enrich the understanding of the glycine molecule and motivate future research on its photo-induced processes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Robert C. Jr Jr Chapleski, Alexander S. Ivanov, Kirk A. Peterson, Vyacheslav S. Bryantsev
Summary: This study focuses on the efficient separation of trivalent lanthanides from minor actinides using soft-donor ligands. Various computational methods are employed to describe the structure of model complexes and predict the selectivity of phosphinic acid ligands in separation. It is found that common density functionals face challenges in accurately predicting selectivity trends, but when used in conjunction with an f-in-core description of metal ions, the correct trend is recovered. This work aims to provide recommendations for more accurate theoretical descriptions of lanthanide/actinide selectivity in the future.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
