Article
Multidisciplinary Sciences
Rachel Garrick, Leeor Kronik, Tim Gould
Summary: A generalized adiabatic connection for any type of range-separated hybrid functional employed within generalized Kohn-Sham theory is presented, which allows for a rigorous distinction between multiplicative exchange and correlation components. The connection is defined in terms of both generalized and conventional KS orbitals, although using only the KS orbitals introduces a small error in practical calculations. The new adiabatic connection is expected to assist in the development and assessment of RSH functionals.
ADVANCED THEORY AND SIMULATIONS
(2022)
Article
Chemistry, Physical
Mikulas Matousek, Michal Hapka, Libor Veis, Katarzyna Pernal
Summary: A multiconfigurational adiabatic connection (AC) formalism is an attractive approach to compute the dynamic correlation within DMRG models. The study investigates the effect of removing the fixed-RDM approximation in AC and finds that lifting this approximation is a viable way toward improving the accuracy of existing AC approximations.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
N. D. Woods, M. T. Entwistle, R. W. Godby
Summary: In the context of inhomogeneous one-dimensional finite systems, recent numerical advances have enabled the computation of the exact coupling-constant dependent exchange-correlation kernel within linear response time-dependent density-functional theory, leading to an improved understanding of ground-state total energies derived from ACFDT. Neglecting frequency dependence in the exact functional while considering both one-shot and self-consistent ACFDT calculations has shown to reliably preserve chemical accuracy, with the spatial structure in the exact functional largely remedying self-interaction issues. The implicit orbitals within a self-consistent ACFDT calculation utilizing the adiabatic exact kernel are remarkably similar to the exact Kohn-Sham orbitals, indicating that the spatial dependence of the functional at zero frequency captures the majority of physics for ground-state total energy.
Review
Chemistry, Physical
Neepa T. Maitra
Summary: Time-dependent density functional theory is a preferred method for calculating spectra and response properties in physics, chemistry, and biology. Its ability to scale to larger systems has made computations possible that were not previously achievable. While simple functional approximations have been successful in handling increasingly complex and interesting systems, there is a growing awareness that these approximations may fail for certain classes of problems. This review discusses the challenges and progress in describing double excitations and charge-transfer excitations, two common obstacles to the theory's application.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Brittany P. Harding, Zachary Mauri, Aurora Pribram-Jones
Summary: Thermal density functional theory is commonly used to simulate warm dense matter, taking into account temperature-dependent effects. However, current methods often approximate temperature-dependent simulations using zero-temperature density functional theory, missing out on the temperature-dependent effects in the exchange-correlation free energy. This study demonstrates and analyzes the temperature-dependent adiabatic connection, leveraging tools based on the approximation of exchange-correlation at zero temperature for finite-temperature cases.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Timothy J. Daas, Derk P. Kooi, Arthur J. A. F. Grooteman, Michael Seidl, Paola Gori-Giorgi
Summary: This study presents a new coupling-strength expansion for the Moller-Plesset perturbation series, accurately evaluating density functionals based on the Hartree-Fock density. Additionally, second-order gradient coefficients are extracted for neutral atoms, revealing a growth pattern that differs from previous literature.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Jiaxin Ning, Donald G. Truhlar
Summary: The geometries, spin states, and bonding characteristics of NdO2 and SmO22+ were studied and compared using spin-orbit-free wave functions. The ground spin states and structures were found to be different for the two molecules, with NdO2 favoring a linear ONdO triplet structure and SmO22+ favoring a linear SmOO2+ quintet structure. The bonding characteristics were investigated using state-averaged complete active-space self-consistent-field (SA-CASSCF) calculations, which showed electron transfer from Nd to O in NdO2 but not between Sm and O in SmO22+.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Materials Science, Multidisciplinary
Ya-Fei Zhang, Zhi Cao, Jian Wang, Ze Liu
Summary: In this study, the H2 adsorption properties on Na-modified 2D B4N monolayer were investigated using density functional theory. The results showed that the 2D B4N monolayer itself has weak adsorption ability for H2 molecules, but the introduction of Na atoms greatly enhances the H2 adsorption energy. The Na/B4N complex can adsorb up to 10 H2 molecules with an average adsorption energy of -0.109 eV/H2, while the 2Na/B4N complex can adsorb up to 20 H2 molecules with an average adsorption energy of -0.116 eV/H2. The obtained H2 adsorption energy falls into the optimal range for mobile hydrogen storage applications. The theoretical study demonstrated that Na-modified 2D B4N monolayer is a promising hydrogen storage material.
RESULTS IN PHYSICS
(2023)
Article
Chemistry, Physical
Ruth H. Tichauer, Dmitry Morozov, Ilia Sokolovskii, J. Jussi Toppari, Gerrit Groenhof
Summary: This study uses multiscale molecular dynamics simulations to investigate the relaxation process of polaritons in tetracene molecules strongly coupled to confined light modes. The results indicate that the relaxation involves vibrationally assisted scattering (VAS) and radiative pumping (RP), both driven by the same molecular vibrations through nonadiabatic coupling between dark states and polaritonic states.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Nanoscience & Nanotechnology
Muhammad Humayun, Habib Ullah, Chao Hu, Mi Tian, Wenbo Pi, Yi Zhang, Wei Luo, Chundong Wang
Summary: Improving the photo-catalytic performance of g-C3N4 by enhancing surface-active sites and optimizing redox couples is crucial. In this study, we synthesized porous g-C3N4 (PCN) through sulfuric acid-assisted chemical exfoliation and modified it with iron(III) meso-tetraphenylpor-phine chloride (FeTPPCl) via wet-chemical method. The resulting FeTPPCl-PCN composite demonstrated exceptional performance in photocatalytic water reduction with significantly improved hydrogen evolution rates compared to pristine PCN. This improvement can be attributed to the enhanced surface-active sites provided by the porous architecture and the well-aligned type-II band heterostructure for efficient charge carrier separation. Through density functional theory simulations, we confirmed the theoretical model of our catalyst and identified the role of electron transfer and electrostatic interactions in hydrogen evolution reaction (HER) activity. The FeTPPCl-PCN composite serves as a promising model for the development of high-efficiency heterostructure photocatalysts for energy applications.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Physics, Fluids & Plasmas
Yuanqing Wang, Wim Ubachs, Cesar A. M. de Moraes, Wilson Marques Jr
Summary: In this study, the spectral distribution of light scattered by microscopic thermal fluctuations in binary mixture gases was investigated experimentally and theoretically. It was found that under given pressure conditions, light mass species act as spectators and do not contribute to the light scattering spectrum, but they influence the motion and relaxation of heavy SF6 molecules.
Article
Energy & Fuels
Xianyao Yan, Yingjie Li, Chunxiao Zhang, Yuzhuo Wang, Jianli Zhao, Zeyan Wang
Summary: The study used density functional theory (DFT) analysis to investigate the water gas shift reaction on the CaO surface and found that it is more likely to proceed along the redox-a pathway. The CaO surface facilitates the spontaneous dissociation of H2O, which is the rate-limiting step of the reaction, and promotes the generation of CO2 with reduced energy barrier. However, the presence of CO32- on the surface may hinder the desorption of CO2 and reduce the enhancement of CaO on the reaction.
Article
Thermodynamics
Elvis do A. Soares, Amaro G. Barreto Jr, Frederico W. Tavares
Summary: This study used classical Density Functional Theory to investigate the adsorption isotherms and structural information of H2 and CH4 fluids in MOF-5. The results show that the adsorption process is influenced by fluid temperature and the shape of the MOF-5 structure. CH4 molecules have stronger interactions with the MOF-5 framework, resulting in a higher adsorbed quantity compared to H2. The study emphasizes the importance of considering the structural properties of adsorbed fluids in MOFs for predicting gas storage capacity at different thermodynamic conditions.
FLUID PHASE EQUILIBRIA
(2023)
Article
Chemistry, Physical
Kimberly J. Daas, Derk P. Kooi, Nina C. Peters, Eduardo Fabiano, Fabio Della Sala, Paola Gori-Giorgi, Stefan Vuckovic
Summary: Noncovalent interactions are crucial in various fields and a methodology for improving pure quantum-chemical simulations of these interactions has been proposed. The methodology combines interpolation, regularization, and spin-scaling strategies to enhance accuracy and competitiveness for noncovalent interactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Biotechnology & Applied Microbiology
Jing Cao, Nan Gao, Yuxuan Bai, Dequan Wang, Ming Wang, Shaokang Shi, Xinyu Yang, Xuri Huang
Summary: The accurate adiabatic and diabatic potential energy surfaces for the two lowest states of He + H-2 were calculated using the Molpro 2012 software package and large basis sets (aug-cc-pV5Z). The adiabatic potential energy surfaces were fitted accurately using the B-spline method, and the diabatic potential energy surfaces of the reaction process were constructed. The study provides insights into the adiabatic process of the reaction system and will be beneficial for histopathology analysis and the study of biological and medical mechanisms.
BIOMED RESEARCH INTERNATIONAL
(2022)
Article
Chemistry, Physical
Sarah Reimann, Alex Borgoo, Jon Austad, Erik I. Tellgren, Andrew M. Teale, Trygve Helgaker, Stella Stopkowicz
Article
Chemistry, Multidisciplinary
Benjamin L. Dale, Nathan R. Halcovitch, Michael J. G. Peach, John M. Griffin
MAGNETIC RESONANCE IN CHEMISTRY
(2019)
Correction
Chemistry, Physical
Christof Holzer, Andrew M. Teale, Florian Hampe, Stella Stopkowicz, Trygve Helgaker, Wim Klopper
JOURNAL OF CHEMICAL PHYSICS
(2019)
Article
Chemistry, Physical
Golda Mensa-Bonsu, Mark R. Wilson, David J. Tozer, Jan R. R. Verlet
JOURNAL OF CHEMICAL PHYSICS
(2019)
Article
Chemistry, Physical
Tom J. P. Irons, Lucy Spence, Gregoire David, Benjamin T. Speake, Trygve Helgaker, Andrew M. Teale
JOURNAL OF PHYSICAL CHEMISTRY A
(2020)
Article
Chemistry, Physical
Golda Mensa-Bonsu, Aude Lietard, David J. Tozer, Jan R. R. Verlet
JOURNAL OF CHEMICAL PHYSICS
(2020)
Article
Chemistry, Physical
Matthew S. Ryley, Michael Withnall, Tom J. P. Irons, Trygve Helgaker, Andrew M. Teale
Summary: This study presents a Gaussian-basis implementation of orbital-free density-functional theory using the trust-region image method for optimization, achieving tight convergence of particle-number constraint and chemical potential. By optimizing density and chemical potential simultaneously, a significant reduction in the number of required iterations for convergence is achieved. The implementation allows for handling of semilocal kinetic-energy functionals in all-electron calculations, facilitating comparison with other quantum-chemical methods and Kohn-Sham density-functional theory.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Physical
Daisy J. Dillon, David J. Tozer
Summary: In this study, the Fermi-Amaldi term is incorporated into approximate DEKS calculations, improving the sensitivity of electronic energy calculations and reducing errors.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Jack T. Taylor, David J. Tozer, Basile F. E. Curchod
Summary: Conical intersections are fundamental to understanding ultrafast, nonadiabatic processes in photochemistry. However, accurately calculating potential energy surfaces near conical intersections remains a challenge for popular electronic structure methods. This study focuses on conical intersections between excited electronic states and evaluates the performance of different methods in describing their topology and topography.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Catherine Mollart, Sarah Holcroft, Michael J. G. Peach, Adam Rowling, Abbie Trewin
Summary: This paper presents a novel method of synthesizing CTF materials through artificial synthesis, which allows for the incorporation of localized structural features resulting from the acid-catalyzed synthetic process. This advancement is crucial for predicting and designing new CTF materials with targeted properties.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Andrew M. Teale, Trygve Helgaker, Andreas Savin, Carlo Adamo, Balint Aradi, Alexei Arbuznikov, Paul W. Ayers, Evert Jan Baerends, Vincenzo Barone, Patrizia Calaminici, Eric Cances, Emily A. Carter, Pratim Kumar Chattaraj, Henry Chermette, Ilaria Ciofini, T. Daniel Crawford, Frank De Proft, John F. Dobson, Claudia Draxl, Thomas Frauenheim, Emmanuel Fromager, Patricio Fuentealba, Laura Gagliardi, Giulia Galli, Jiali Gao, Paul Geerlings, Nikitas Gidopoulos, Peter M. W. Gill, Paola Gori-Giorgi, Andreas Gorling, Tim Gould, Stefan Grimme, Oleg Gritsenko, Hans Jorgen Aagaard Jensen, Erin R. Johnson, Robert O. Jones, Martin Kaupp, Andreas M. Koster, Leeor Kronik, Anna Krylov, Simen Kvaal, Andre Laestadius, Mel Levy, Mathieu Lewin, Shubin Liu, Pierre-Francois Loos, Neepa T. Maitra, Frank Neese, John P. Perdew, Katarzyna Pernal, Pascal Pernot, Piotr Piecuch, Elisa Rebolini, Lucia Reining, Pina Romaniello, Adrienn Ruzsinszky, Dennis R. Salahub, Matthias Scheffler, Peter Schwerdtfeger, Viktor N. Staroverov, Jianwei Sun, Erik Tellgren, David J. Tozer, Samuel B. Trickey, Carsten A. Ullrich, Alberto Vela, Giovanni Vignale, Tomasz A. Wesolowski, Xin Xu, Weitao Yang
Summary: This paper provides an informal review and discussion on the history, present status, and future of density-functional theory (DFT) by 70 workers in the field. The format of a roundtable discussion allowed participants to express their views through 302 individual contributions to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper offers a comprehensive snapshot of DFT in 2022.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Lei Ji, Stefan Riese, Alexander Schmiedel, Marco Holzapfel, Maximillian Fest, Joern Nitsch, Basile F. E. Curchod, Alexandra Friedrich, Lin Wu, Hamad H. Al Mamari, Sebastian Hammer, Jens Pflaum, Mark A. Fox, David J. Tozer, Maik Finze, Christoph Lambert, Todd B. Marder
Summary: Reversible conversion between excited states is crucial in various photophysical phenomena. By conducting experiments and calculations, we discovered that the energy gaps and barriers among the locally-excited and charge-transfer states in 1-(pyren-2'-yl)-o-carborane are negligible, making all three states accessible at room temperature. Furthermore, the internal-conversion and reverse internal-conversion processes occur much faster than radiative decay, resulting in the same lifetimes and thermodynamic equilibrium of the two states.
Article
Chemistry, Inorganic & Nuclear
Andrew J. Valentine, Ana M. Geer, Laurence J. Taylor, Andrew M. Teale, Katherine E. Wood, Huw E. L. Williams, William Lewis, Stephen P. Argent, Jonathan McMaster, Deborah L. Kays
Summary: The effect of para-substitution on a series of m-terphenyl lithium complexes has been investigated. X-ray crystallography shows structural similarity, while in-depth NMR spectroscopic studies reveal notable electronic differences, correlated with the nature of the substituents.
DALTON TRANSACTIONS
(2021)
Meeting Abstract
Chemistry, Multidisciplinary
Trygve Helgaker, Matthew Ryley, Andrew Teale
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Physical
Golda Mensa-Bonsu, David J. Tozer, Jan R. R. Verlet
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2019)