Article
Multidisciplinary Sciences
Rafael B. Araujo, Gabriel L. S. Rodrigues, Egon Campos dos Santos, Lars G. M. Pettersson
Summary: This study demonstrates that correction from higher-level calculations on small metal clusters can improve adsorption energies and barriers in periodic band structures. The results outperform widely used functionals in surface science evaluations when benchmarked against reliable experimental data.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Sara Giarrusso, Pierre-Francios Loos
Summary: This study calculates the functionals of the ground state and two excited states of the asymmetric Hubbard dimer, and finds that there is a specific relationship between the energy and functional of each state.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
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
Daniele Toffoli, Matteo Quarin, Giovanna Fronzoni, Mauro Stener
Summary: This benchmark study investigates the vertical excitation energies and oscillator strengths of 17 boron-dipyrromethene (BODIPY) structures with different ring sizes and substituents. The results obtained from time-dependent density functional theory (TDDFT) and delta-self-consistent-field (Delta SCF) methods, using various exchange correlation kernels, are compared with experimental excitation energies. The study shows that the time-independent Delta SCF DFT method, particularly when combined with hybrid PBE0 and B3LYP functionals, outperforms TDDFT and rivals more computationally expensive wave function based methods in terms of accuracy.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Daniil Khokhlov, Aleksandr Belov
Summary: The study utilized DSRG-MRPT2 method to investigate the excited states of carotenoids, showing reasonable agreement with experimental data after adjusting the DSRG flow parameter.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Jan Kloppenburg, Livia B. Partay, Hannes Jonsson, Miguel A. Caro
Summary: A Gaussian approximation machine learning interatomic potential for platinum is developed based on density-functional theory (DFT) data. The potential exhibits excellent transferability and agreement with DFT in various properties such as bulk elasticity, surface energetics, and nanoparticle stability. It provides state-of-the-art accuracy at a low computational cost. Two examples are presented to demonstrate the potential's capability in modeling Pt systems: the pressure-temperature phase diagram of Pt calculated using nested sampling and a study of the spontaneous crystallization of a large Pt nanoparticle based on classical dynamics simulations over several nanoseconds.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Thomas Froitzheim, Stefan Grimme, Jan-Michael Mewes
Summary: This study examines the performance of TDA-DFT methods in predicting Delta EST values, finding that calculating Delta EST at the ground-state structure is the most effective strategy but it introduces systematic deviations. More rigorous approaches, although more accurate, have larger errors.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Biochemistry & Molecular Biology
Monica Mendes, Fabris Kossoski, Ana Lozano, Joao Pereira-da-Silva, Rodrigo Rodrigues, Joao Ameixa, Nykola C. Jones, Soren Hoffmann, Filipe Ferreira da Silva
Summary: In this study, absolute photoabsorption cross sections for gas-phase 2- and 5-bromopyrimidine in the 3.7-10.8 eV energy range were reported through a combination of experimental and theoretical approaches. The cross sections of the two bromopyrimidines are similar below 7.3 eV but diverge at higher energies. The main absorption band is broader and shifted to higher energies in both bromopyrimidines compared to bromobenzene, with significant differences observed in the vibrational structures and Rydberg states.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Moritz Thurlemann, Sereina Riniker
Summary: Electronic structure methods offer accurate predictions but with high computational costs. Empirical methods are cheaper but have inherent approximations and data dependence. Machine learning force fields exacerbate limitations related to training data. A proposed hybrid model combines machine learning and classical force fields, providing accuracy and flexibility.
Article
Chemistry, Physical
Daniele Loco, Isabelle Chataigner, Jean-Philip Piquemal, Riccardo Spezia
Summary: Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy that complements experimental studies to understand reaction mechanisms. This research benchmarked various computational approaches for predicting energy barriers in six Diels-Alder reactions of increasing complexity. The results showed that using economical Density Functional Theory methods combined with empirical dispersion corrections can provide high-quality results with minimal computational effort. This simulation protocol opens new prospects for studying Diels-Alder reactions with explicit solvent using hybrid QM/MM molecular dynamics simulations.
Article
Chemistry, Physical
Diptarka Hait, Martin Head-Gordon
Summary: This article discusses the use of state-specific orbital optimized (OO) DFT approaches as an alternative to TDDFT for modeling electronic excited states, highlighting their advantages and limitations compared to TDDFT and emphasizing the importance of modern developments in addressing these limitations. Several successful applications of OO-DFT methods are presented to demonstrate their practical efficacy in computing challenging electronic excitations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Zhe-Ning Chen, Tonghao Shen, Yizhen Wang, Igor Ying Zhang
Summary: Describing catalytic selectivity accurately remains a challenge for theoretical simulations, with the lack of well-defined benchmark sets. This study introduced a test set based on selective hydrogenation reactions, revealing the effectiveness of certain functionals in addressing complex correlation effects. The newly proposed xDH method, scsRPA, demonstrated unprecedented accuracy and versatility in predicting kinetic selectivity for catalytic reactions.
Article
Chemistry, Physical
Shashikant Kumar, Edgar Landinez Borda, Babak Sadigh, Siya Zhu, Sebastian Hamel, Brian Gallagher, Vasily Bulatov, John Klepeis, Amit Samanta
Summary: This study proposes a simplified method for accurately modeling the kinetic energy density of any system. The method utilizes a dictionary of functional forms for local and nonlocal contributions, and employs linear regression to calculate appropriate coefficients. It also introduces a basis function expansion to handle the nonlocal terms.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Sapphire Armstrong, Thomas Malcomson, Andy Kerridge
Summary: In this study, time dependent density functional theory (TDDFT) calculations were used to investigate the excited states of the uranyl dication, UO22+. The electronic structures of the excited states were compared to the ground state, and the Quantum Theory of Atoms in Molecules (QTAIM) was applied to quantify the changes in bond covalency upon electronic excitation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
Nongnuch Artrith, Jose Antonio Garrido Torres, Alexander Urban, Mark S. Hybertsen
Summary: This article presents a systematic method to determine parameters and optimize the errors of semilocal density-functional theory (DFT) methods for transition-metal oxides phase diagrams. By considering thermochemical data of a set of compounds and using leave-one-out cross validation, the proposed correction terms reduce the errors in the formation energies of binary and ternary oxides by up to 75% and achieve an error reduction of 30% using a simplified scheme.
PHYSICAL REVIEW MATERIALS
(2022)