Article
Chemistry, Physical
Wenna Ai, Wei-Hai Fang, Neil Qiang Su
Summary: The short-range corrected reduced density matrix functional omega P22 is developed to utilize the advantages of functionals in KS-DFT and RDMFT without double-counting, outperforming other 1-RDM functionals in tests of thermochemistry, nonbonded interactions, and bond dissociation energy. Omega P22 shows less systematic error for systems involving fractional spins and can accurately predict the energies for different single and multiple bonds, filling a gap left by commonly used KS-DFT and RDMFT functionals.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Ivor Loncaric, Maite Alducin, J. Inaki Juaristi
Summary: Despite the success of density functional theory, there are still cases where current functionals fail to describe certain materials. This study adds to the list by showing that the interaction between O-2 and Ag(110) cannot be properly described by popular functionals. The authors provide clues for the development of a functional that can accurately describe this and similar systems.
Article
Optics
Mekhrdod S. Kurboniyon, Bibo Lou, Umar Zafari, Farhod Rahimi, Alok M. Srivastava, Tomoyuki Yamamoto, Mikhail G. Brik, Chong-Geng Ma
Summary: In this study, first-principles calculations were conducted to investigate the geometric and electronic structures and optical transition energies of K2SiF6:Mn4+. A state-of-art calculation scheme was developed using comprehensive evaluation of exchange-correlation functionals, resulting in better agreement with experimental results. However, the conventional approach failed to accurately evaluate the optical transition energies, indicating the need for new calculation techniques in the field of optical materials.
JOURNAL OF LUMINESCENCE
(2023)
Article
Chemistry, Multidisciplinary
Kai Trepte, Johannes Voss
Summary: This paper presents an empirical approach to improve the estimation of surface chemical reaction energetics. By optimizing the exchange-correlation functional with a combination of reference data and physical model constraints, the proposed method achieves accurate predictions not only for surface chemistry simulations but also for gas phase reactions and bulk lattice constants and elastic properties.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Takumi Kariya, Hayato Hasegawa, Taro Udagawa, Yusaku Inada, Kyoko Nishiyama, Mieko Tsuji, Tasuku Hirayama, Tatsuo Suzutani, Naoki Kato, Shingo Nagano, Hideko Nagasawa
Summary: This study investigates the role of the absolute configuration of the C-6 carbon of the substrate polyene in the stereocontrol of the intramolecular Diels-Alder reaction (IMDA). The results show that Fsa2 exhibits consistent stereoselectivity, while Phm7 shows different stereoselectivity depending on the configuration of the 6-methyl group. The study also discovers a unique relationship between the stereochemistry of decalins and their antibacterial activity.
Article
Chemistry, Physical
Wenna Ai, Wei-Hai Fang, Neil Qiang Su
Summary: This study focuses on the range-separated correlation in long-range corrected hybrid functionals, presenting a theory on its derivation and proving its reliability and effectiveness. The new functional proposed in this work outperforms the traditional LC-BLYP method in various tests and maintains important properties of the XC potential.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Review
Energy & Fuels
Guoxin Zhuang, Jiawei Yan, Yonglin Wen, Zanyong Zhuang, Yan Yu
Summary: Sunlight-driven catalytic reactions are crucial for energy and environmental issues. Transition metal oxides (TMOs) and chalcogenides (TMCs) are popular photocatalysts due to their stability, cost-efficiency, and catalytic activity. Downsizing them to 2D materials allows for tuning their properties, but more research is needed on their form-to-function relationship and synthesis mechanisms.
Article
Chemistry, Physical
Caspar Jonas Schattenberg, Martin Kaupp
Summary: Exchange-correlation functionals dependent on local kinetic energy tau have been widely used in nuclear shielding calculations. The introduction of a proper current-density functional version tau(D) eliminates gauge dependence and unphysical contributions, providing improved accuracy for certain functionals in nuclear shielding calculations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
D. Koulentianos, V. Carravetta, R. C. Couto, J. Andersson, A. Hult Roos, R. J. Squibb, M. Wallner, J. H. D. Eland, M. Simon, H. Agren, R. Feifel
Summary: Using a magnetic bottle multi-electron time-of-flight spectrometer in combination with synchrotron radiation, researchers have successfully identified double-core-hole pre-edge and continuum states involving the K-shell of carbon atoms in n-butane. By detecting coincidence events of ejected core electrons and emitted Auger electrons, the main observed spectral features have been assigned based on calculations of excitation energies and intensities. The combination of multi-configurational self-consistent field calculations and static exchange techniques proves to be a viable approach in analyzing double-core-hole spectra.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Juan Felipe Huan Lew-Yee, Jorge M. del Campo, Mario Piris
Summary: The relative stability of the singlet, triplet, and quintet spin states of iron(II) porphyrin (FeP) is a challenge for electronic structure methods. Different methods lead to conflicting predictions, with some suggesting a quintet ground state and others suggesting a triplet ground state. The Global Natural Orbital Functional (GNOF), along with the Piris Natural Orbital Functionals (PNOFs), provides a balanced treatment of static and dynamic correlations and allows for a more accurate understanding of the stability order of FeP states.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Medicinal
Ryuhei Harada, Rikuri Morita, Yasuteru Shigeta
Summary: The free-energy profile of a compound is crucial in evaluating membrane permeation and can be calculated using molecular dynamics simulations. However, existing methods often fail to sample rare events in membrane permeation accurately. In this study, a hybrid conformational search method combining rare-event sampling methods and Markov state models was proposed to calculate the free-energy profiles and membrane permeability of seven compounds with good correlation to experimental measurements.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Chemistry, Physical
Maria V. Pagliaro, Cuilian Wen, Baisheng Sa, Baoyu Liu, Marco Bellini, Francesco Bartoli, Sanjubala Sahoo, Ramesh K. Singh, S. Pamir Alpay, Hamish A. Miller, Dario R. Dekel
Summary: Anion-exchange membrane fuel cells (AEMFCs) are a promising electrochemical power generation technology that may be used in stationary power supply and mobile applications like electric vehicles. One challenge with AEMFCs is the development of catalysts with improved activities to reduce the current over potential losses. This study demonstrates that the alkaline hydrogen oxidation reaction (HOR) activity of palladium nanoparticles can be enhanced through strong interactions with transition metal oxides.
Article
Chemistry, Physical
Maria V. Pagliaro, Cuilian Wen, Baisheng Sa, Baoyu Liu, Marco Bellini, Francesco Bartoli, Sanjubala Sahoo, Ramesh K. Singh, S. Pamir Alpay, Hamish A. Miller, Dario R. Dekel
Summary: This study investigates how the alkaline HOR activity of palladium nanoparticles can be enhanced through interactions with transition metal oxides. The results show that Pd-RuO2/C displays the highest HOR surface-specific activity among the materials analyzed.
Article
Nanoscience & Nanotechnology
Yaxin Shi, Haoli Pan, Junyi Xia, Can Li, Yinyan Gong, Lengyuan Niu, Xinjuan Liu, Chang Q. Sun, Shiqing Xu
Summary: The correlation factor of d electron density of transition metal ions was developed to correlate with preparation methods in order to improve the electrocatalytic activities of (CoFeAlx)3O4 specimens. This strategy showed favorable linear relationships with theoretical overpotentials and altered the volume of systems, leading to improved catalytic activities. Adjusting the correlation factor with suitable preparation methods could be applied to design highly efficient catalysts.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
C. Andre Ohlin
Summary: Density functional theory was used to explore the factors governing the substitution of group 4B-12B metals into the decaniobate framework, accurately predicting substitution patterns and guiding future synthetic efforts. The calculations also revealed trends and potential synthetic approaches for a large series of [MNb9O28](x-) clusters. OPBE/def2-tzvp correctly predicted favored spin states of known substituted decametalates.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Ahmed O. Elnabawy, Roberto Schimmenti, Ang Cao, Jens K. Norskov
Summary: The choice of Cu/ZnO/Al2O3 as the industrial catalyst for methanol synthesis is due to the strong metal support interactions. In this study, DFT calculations reveal that only ZnO and Ga2O3 can partially cover the Cu surface and modify it without diluting the necessary Cu sites for reactants' activation, while other oxides are either too stable or readily cover the Cu surface completely.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Katja Li, Sarah G. Shapel, Degenhart Hochfilzer, Jakob B. Pedersen, Kevin Krempl, Suzanne Z. Andersen, Rokas Sazinas, Mattia Saccoccio, Shaofeng Li, Debasish Chakraborty, Jakob Kibsgaard, Peter C. K. Vesborg, Jens K. Norskov, Ib Chorkendorff
Summary: The current density and ammonia formation rates were significantly improved by synthesizing high surface area Cu electrodes through hydrogen bubbling templating (HBT) on Ni foam substrates. Increasing the electrolyte salt concentration was found to enhance the stability of the system.
ACS ENERGY LETTERS
(2022)
Article
Chemistry, Physical
Lan Zhou, Hao Li, Yungchieh Lai, Matthias Richter, Kevin Kan, Joel A. Haber, Sara Kelly, Zhenbin Wang, Yubing Lu, R. Soyoung Kim, Xiang Li, Junko Yano, Jens K. Norskov, John M. Gregoire
Summary: Guided by computational screening and high-throughput experiments, rutile CoSb2O6 has been identified as a promising precious-metal-free electrocatalyst for oxygen reduction in acidic media, demonstrating operational stability and favorable energetics.
ACS ENERGY LETTERS
(2022)
Article
Multidisciplinary Sciences
Ang Cao, Vanessa J. Bukas, Vahid Shadravan, Zhenbin Wang, Hao Li, Jakob Kibsgaard, Ib Chorkendorff, Jens K. Norskov
Summary: This article provides an overview of recent experimental results on new promoters for ammonia synthesis and develops a model to explain their working principles. The authors identify a new promotion mechanism mediated by the coupling between adsorption and spin polarization on the surface atoms of magnetic catalysts, resulting in a lowering of activation energy.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Sudarshan Vijay, Georg Kastlunger, Karen Chan, Jens K. Norskov
Summary: Linear scaling relations are important in understanding catalytic activity and selectivity, but not all small molecule adsorbates have linearly scaling chemisorption energies. This study found that the chemisorption energies of carbon and oxygen on transition metal surfaces do not scale due to differences in the re-normalized adsorbate valence energies. A model and a general descriptor were developed to determine if two adsorbates are likely to scale with each other.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Debasish Chakraborty, Thomas Erik Lyck Smitshuysen, Arvin Kakekhani, Sebastian Pirel Fredsgaard Jespersen, Sayan Banerjee, Alexander Krabbe, Nicolai Hagen, Hugo Silva, Justus Just, Christian Danvad Damsgaard, Stig Helveg, Andrew M. Rappe, Jens K. Norskov, Ib Chorkendorff
Summary: In this study, we have successfully reduced the loading of precious metal catalysts by choosing appropriate transition metal/support pairs and utilizing the reversible atomization-nanoparticulate formation mechanism. The results show that the metal Pt can undergo reversible transformation between ionic and nanoparticle forms under different oxidation-reduction conditions. The study also identifies favorable adsorption sites for reversible Pt adsorption and proposes a re-activation mechanism for atomized Pt based on gases present during the reaction.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Melissa E. Kreider, G. T. Kasun Kalhara Gunasooriya, Yunzhi Liu, Jose A. Zamora Zeledon, Eduardo Valle, Chengshuang Zhou, Joseph H. Montoya, Alessandro Gallo, Robert Sinclair, Jens K. Norskov, Michaela Burke Stevens, Thomas F. Jaramillo
Summary: Strategies for improving the performance of nonprecious metal catalysts for the oxygen reduction reaction (ORR) are crucial for cost-effective deployment of fuel cell devices. In this study, the authors utilized two methods, increasing the number of active sites and improving the intrinsic activity, to enhance the performance of MnSb2O6 as an ORR catalyst. Experimental and theoretical approaches were employed to investigate the factors affecting the catalytic activity, revealing that the addition of Cr significantly improved the activity of MnSb2O6. This study provides insights into the intrinsic and extrinsic factors that govern ORR performance.
Article
Chemistry, Physical
Shaofeng Li, Yuanyuan Zhou, Katja Li, Mattia Saccoccio, Suzanne Z. Andersen, Jakob B. Pedersen, Xianbiao Fu, Vahid Shadravan, Debasish Chakraborty, Jakob Kibsgaard, Peter C. K. Vesborg, Jens K. Norskov, Ib Chorkendorff
Summary: In this study, a highly efficient lithium-mediated ammonia synthesis process was proposed, which could enhance the ammonia production rate and faradaic efficiency by forming a uniform solid-electrolyte interphase (SEI) layer on a porous copper electrode.
Article
Multidisciplinary Sciences
Xianbiao Fu, Jakob B. Pedersen, Yuanyuan Zhou, Mattia Saccoccio, Shaofeng Li, Rokas Salinas, Katja Li, Suzanne Z. Andersen, Aoni Xu, Niklas H. Deissler, Jon Bjarke Valbaek Mygind, Chao Wei, Jakob Kibsgaard, Peter C. K. Vesborg, Jens K. Norskov, Ib Chorkendorff
Summary: Ammonia is an important substance in various industries and can also be used as a carbon-free fuel. A new approach using lithium-mediated nitrogen reduction has shown promise in the electrochemical synthesis of ammonia. In this study, a continuous-flow electrolyzer with gas diffusion electrodes was used, and a platinum-gold alloy catalyst was found to be more stable and efficient for the reaction. The results showed a high faradaic efficiency for ammonia production and energy efficiency at optimal conditions.
Article
Chemistry, Physical
Ang Cao, Jens K. Norskov
Summary: Using density functional theory calculations, this work demonstrates that controlling the spin state of magnetic metal surfaces significantly impacts their chemical properties. The adsorption energy of various adsorbates is shown to be stronger on non-spin polarized surfaces compared to spin polarized ground state surfaces. This finding is consistent for Fe, Co, and Ni surfaces, as well as three commonly used exchange-correlation functionals. The origin of this effect is discussed in terms of surface electronic structure, and a simple model based on the d-band model of adsorption is proposed to explain the phenomenon. The study also explores the potential of utilizing spin effects to manipulate surface reactivity, such as through the addition of a metal promotor.
Article
Chemistry, Multidisciplinary
Naiwrit Karmodak, Jens K. Norskov
Summary: In this study, a computational catalyst-screening method was designed to identify potentially interesting single-atom catalysts (SACs) and di-atom catalysts (DACs) for the O-2 reduction reaction (ORR). Four SACs and fifteen DACs with high estimated catalytic activity were identified, some of which showed high stability in both acidic and alkaline media.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Vahid Shadravan, Ang Cao, Vanessa J. Bukas, Mette K. Gronborg, Christian D. Damsgaard, Zhenbin Wang, Jakob Kibsgaard, Jens K. Norskov, Ib Chorkendorff
Summary: This study presents a new class of ruthenium-based catalysts promoted with metallic cesium using an in situ preparation technique. The in situ promoted catalysts show significantly higher activity, smaller apparent activation energy, and less susceptibility to H-2 poisoning compared to the ones prepared by traditional ex situ promotion methods. The findings suggest that this new technique can lead to a more sustainable and decentralized ammonia synthesis process.
ENERGY & ENVIRONMENTAL SCIENCE
(2022)
Article
Chemistry, Physical
Christina Susan Abraham, Megha Anand, Sara R. Kelly, Zhenbin Wang, Jens K. Norskov
Summary: The study indicates that surface modification of niobium pentaoxide with transition metal doping can improve its conductivity, which is generally effective in the case of transition metal oxides, but has negligible influence on the ORR activity of the doped systems.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Michaela Burke Stevens, Megha Anand, Melissa E. Kreider, Eliza K. Price, Jose Zamara Zeledon, Liang Wang, Jiayu Peng, Hao Li, John M. Gregoire, Jens Hummelshoj, Thomas F. Jaramillo, Hongfei Jia, Jens K. Norskov, Yuriy Roman-Leshkov, Yang Shao-Horn, Brian D. Storey, Santosh K. Suram, Steven B. Torrisi, Joseph H. Montoya
Summary: In this article, the results of a research consortium focused on advancing understanding of oxygen reduction reaction (ORR) catalysis are highlighted. Collaborations between different institutions and scientific disciplines have provided unique insights into fuel cell catalysts. The article emphasizes the importance of material designs, catalyst durability, and the role of emerging artificial intelligence tools in accelerating the design and discovery of fuel cell catalysts.
ENERGY & ENVIRONMENTAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Jose A. Zamora Zeledon, G. T. Kasun Kalhara Gunasooriya, Gaurav A. Kamat, Melissa E. Kreider, Micha Ben-Naim, McKenzie A. Hubert, Jaime E. Aviles Acosta, Jens K. Norskov, Michaela Burke Stevens, Thomas F. Jaramillo
Summary: Understanding material-property relationships in mixed-element catalyst systems is crucial for renewable electrochemical energy technologies. In this study, the nature and dynamics of highly active Ag-MnOx catalyst surfaces for ORR were investigated using an experimental-theoretical approach. Well-mixed Ag-Mn co-deposited thin films were synthesized and showed enhanced specific activity compared to pure Ag. The enhancement was attributed to the tuned d-band of the material surfaces resulting from the optimal hybridization of electronic structures in specific Ag and MnOx geometries.
ENERGY & ENVIRONMENTAL SCIENCE
(2022)
