Article
Physics, Condensed Matter
Miaomiao Jin, Marat Khafizov, Chao Jiang, Shuxiang Zhou, Chris A. Marianetti, Matthew S. Bryan, Michael E. Manley, David H. Hurley
Summary: This study examines the efficacy of an embedded-atom empirical interatomic potential in computing vibrational properties of crystals, finding significant discrepancies in dealing with optical branches, leading to an overestimation of phonon lifetime and thermal conductivity. The empirical potential needs further optimization for robust prediction of thermal conductivity in perfect crystals and in the presence of complex defects.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2021)
Article
Chemistry, Physical
Monu, Binod Kumar Oram, Biman Bandyopadhyay
Summary: A DFT-based methodology has been used to construct potential energy surfaces for H2S and water clusters, showing good agreement with experimental and theoretical results. The method accurately identifies stable conformers and interactions in the clusters, with energy gaps between most and least stable conformers within a narrow range.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Liangfei Fu, Shuo Yang, Dong H. Zhang
Summary: Full-dimensional, ab initio-based many-body potential energy surfaces and dipole moment surfaces for SO2(H2O)(n) (n = 1,2) complexes were constructed using the neural network method. The databases consisted of 11,952, 79,882, and 84,159 ab initio energies for the 1-body, 2-body, and 3-body PESs, respectively. The dipole moments were calculated at the MP2/AVTZ level. The fidelity of these PESs was examined by comparing harmonic frequencies and dissociation energies with ab initio results.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Sergei Manzhos, Tucker Carrington
Summary: This review focuses on the development of neural network-based methods for constructing molecular potential energy surfaces that explicitly include all many-body contributions. Various approaches including single NN PES fitting and more complex methods are discussed, highlighting the effectiveness of NNs in building representations with low-dimensional functions and emerging tools for accurate PESs in relatively large molecular systems.
Article
Chemistry, Physical
Toyin Shittu, Mohammednoor Altarawneh
Summary: This study investigates the mechanism and pathways of methanethiol decomposition on a defect CeO2 surface using density functional theory calculations. The results provide a detailed atomistic understanding of the desulfurization capacity of ceria surfaces.
APPLIED SURFACE SCIENCE
(2022)
Article
Biochemical Research Methods
Amanda R. Bubas, Evan Perez, Luke J. Metzler, Scott D. Rissler, Michael J. Van Stipdonk
Summary: Electrospray ionization (ESI) is used to generate gas-phase uranyl complexes for tandem mass spectrometry studies. Experimental and DFT calculations show dissociation of nitrate ligands leads to interesting product ions, with O-2 and NO2 being eliminated from the complexes.
JOURNAL OF MASS SPECTROMETRY
(2021)
Article
Biochemical Research Methods
Amanda R. Bubas, Evan Perez, Luke J. Metzler, Scott D. Rissler, Michael J. Van Stipdonk
Summary: This study investigates the collision-induced dissociation of [UO2(NO3)(3)](-) and [UO2(NO3)(2)(O-2)](-), as well as the CID of [UO2(NO3)(O-2)](-) and the resulting product ions. DFT calculations identified pathways for the generation of product ions, revealing that the composition of [UO2(O)(NO2)](-) is [UO2(O)(NO2)](-) rather than [UO2(NO3)](-).
JOURNAL OF MASS SPECTROMETRY
(2021)
Article
Chemistry, Physical
Keaton Prather, Jonathan T. Stoffel, Emily Y. Tsui
Summary: This perspective discusses how reduction, oxidation, and electrostatics on the surface of colloidal semiconductor nano-crystals (NCs) contribute to their electronic properties, including photoluminescence quenching or brightening and shifts in band edge potentials. It highlights recent efforts in combining spectroscopic, electrochemical, and computational methods to characterize redox-active surface sites and trap states and explores future opportunities in this field.
CHEMISTRY OF MATERIALS
(2023)
Article
Multidisciplinary Sciences
Annette Pietzsch, Johannes Niskanen, Vinicius Vaz da Cruz, Robby Buechner, Sebastian Eckert, Mattis Fondell, Raphael M. Jay, Xingye Lu, Daniel McNally, Thorsten Schmitt, Alexander Foehlisch
Summary: The fluctuating hydrogen bond network in liquid water was studied using resonant inelastic X-ray scattering, revealing a diverse range of molecular potential energy surfaces. A comparison with the gas phase potentials was made, and it was found that the liquid phase potentials varied from weak to strongly distorted interactions.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Inorganic & Nuclear
Xiao-Cheng Xu, Jun-Jie Song, Han-Shi Hu
Summary: The hydrogen bonds in water clusters are enhanced within the confinement effect of the U-20 cage. The confined water clusters can form hydrogen bonds with the internal oxygen atoms of U-20, resulting in significant conformational changes. The hydrogen bonds in confined water clusters are shorter and show better hydrogen bond patterns compared to free water clusters. Electron transferring from U-20 to confined water clusters enhances the hydrogen bond interactions by making the oxygen atoms more negatively charged and the hydrogen atoms more positively charged.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Huong T. T. Ta, Hao V. Bui, Viet-Huong Nguyen, A. Kiet Tieu
Summary: DFT calculations were performed to understand the atomic mechanisms of SiO2 film growth from SiCl4 and H2O precursors on TiO2 surfaces. The results showed that surface hydroxylation facilitated the initial reaction and reduced the production of adsorbed atomic chlorine. Recombination of the HCl by-product with the surface may lead to the creation of atomic chlorine.
SURFACES AND INTERFACES
(2023)
Review
Chemistry, Analytical
Alfred B. Anderson
Summary: This article provides an overview of three models for calculating activation energies and reversible potentials for oxidation and reduction reactions involving protons at the electrochemical interface, with a focus on one of them. The models either incorporate the electrode potential or use surface charging to set the potential. The simplest theories come in two forms, with empirical components and inputs from experimental data and adsorbate energies.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Tomas Rauch, Miguel A. L. Marques, Silvana Botti
Summary: Understanding the electronic properties of matter is crucial for proposing useful applications, as accurate approximations to the exchange-correlation functional of density functional theory may become computationally expensive for modeling hybrid organic/inorganic systems. The study of the local modified Becke-Johnson exchange-correlation potential for calculated ionization potentials is important for band alignment in composite systems. Demonstrating the potential's application in the electronic structure calculation of a composite semiconductor/molecule system shows its accuracy and usefulness.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Multidisciplinary
Hao Wu, Yanlin Fu, Wenrui Dong, Bina Fu, Dong H. Zhang
Summary: An accurate global full-dimensional machine learning-based potential energy surface (PES) of the simplest Criegee intermediate (CH2OO) reaction with water monomer was developed. The PES covers reactants to hydroxymethyl hydroperoxide (HMHP) intermediates and different end product channels, facilitating reliable and efficient kinetics and dynamics calculations.
Article
Chemistry, Physical
Yanhui Zhang, Stefano Sanvito
Summary: Understanding surface reactivity is crucial in various fields, and the surface reactions of ZrB2 exposed to harsh aerospace environments were studied using density functional theory and nudged elastic band methods. It was found that dissociative adsorption of O-2 dominates the reactivity of ZrB2 surfaces, while the reactions of H2O and CO are less active on Zr-surfaces and even less on B-terminated ones. Additionally, the reaction of O-2 and CO was shown to induce strong surface reconstruction at B-surfaces.
APPLIED SURFACE SCIENCE
(2021)
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)