Article
Chemistry, Physical
Tim Gould, Zahed Hashimi, Leeor Kronik, Stephen G. Dale
Summary: In this paper, a simple correction method based on rigorous ensemble density functional theory is introduced, which makes the HOMO-LUMO gap exact in principle and significantly improves accuracy in practice. The method predicts different values for singlet-singlet and singlet-triplet excitations, and the quality of excitation energies is similar to time-dependent density functional theory.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Xinming Qin, Honghui Shang, Jinlong Yang
Summary: The NAO2GTO scheme is an efficient method for evaluating ERIs over NAOs with GTOs. However, it may affect the accuracy and convergence of hybrid functional calculations. To solve this issue, we propose using fitted orbitals as a new numerical basis. We provide an efficient implementation of analytical gradients for HFX energy in periodic HSE06 calculations with fitted NAOs.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Physical
Sheng Chen, Kai Wu, Wei Hu, Jinlong Yang
Summary: In this study, the ACE-ISDF formulation is derived for hybrid functional calculations in unrestricted and noncollinear spin DFT with plane waves and periodic boundary conditions. Improved ACE-ISDF low-rank approximations are proposed to further reduce the computational cost for spin-noncollinear systems. Numerical results demonstrate the efficiency and accuracy of the ACE-ISDF method in investigating the electronic and magnetic properties of periodic magnetic systems.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Kanun Pokharel, Christopher Lane, James W. Furness, Ruiqi Zhang, Jinliang Ning, Bernardo Barbiellini, Robert S. Markiewicz, Yubo Zhang, Arun Bansil, Jianwei Sun
Summary: The crystal, electronic, and magnetic structures of La2-xSrxCuO4 (LSCO) for different doping levels were studied using various density functional approximations. It was found that the meta-generalized gradient approximation (meta-GGA) class of functionals performed well in describing the properties of LSCO, while the local spin-density approximation, generalized gradient approximation, and hybrid density functional failed to capture the metal-insulator transition under doping.
NPJ COMPUTATIONAL MATERIALS
(2022)
Article
Chemistry, Physical
Kai Wu, Xinming Qin, Wei Hu, Jinlong Yang
Summary: By combining the ACE operator and ISDF decomposition, the new ACE-ISDF algorithm offers a more efficient method for hybrid functional calculations in periodic systems with k-point sampling in reciprocal space. This algorithm significantly reduces the time complexity and memory consumption compared to the standard method for systems with a plane-wave basis set.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Multidisciplinary Sciences
Inbar Seroussi, Gadi Naveh, Zohar Ringel
Summary: Deep neural networks (DNNs) have complex structures, making direct microscopic analysis difficult. However, by identifying slow variables that average the behavior of fast variables, the authors have found a similar scale separation in finite deep convolutional neural networks and fully connected networks. They show that DNN layers couple through the second cumulant of their activations and pre-activations, which fluctuate in a Gaussian manner. The resulting thermodynamic theory of deep learning provides accurate predictions and new ways to understand DNNs.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Yixiang Cao, Mathew D. Halls, Richard A. Friesner
Summary: The study demonstrates that using the pseudospectral method for TDDFT excited state gradient calculations results in higher accuracy and efficiency. Both excited state geometry optimizations and fullerene calculations show significant speedups with the pseudospectral method.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Inorganic & Nuclear
Zheng Zhang, Hadiah Fattal, Tielyr D. Creason, Mehran Amiri, Alexander Roseborough, Isaiah W. Gilley, May Nyman, Bayram Saparov
Summary: Recently, the solution chemistry of a model indium halide system, methylammonium (MA)-In-Br, was studied using a combination of various techniques. The results showed that under different loading ratios of reactants, indium could form either octahedral or tetrahedral anions in solution, or a combination of both. The understanding of the solution chemistry of this system led to the targeted crystallization of two novel compounds. These findings highlight the importance of understanding the solution chemistry of multinary metal halide systems for the discovery of functional materials for practical applications.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Artem Mitrofanov, Nikolai Andreadi, Vadim Korolev, Stepan Kalmykov
Summary: Actinide chemistry often faces limitations with modern theoretical tools due to high computational costs and relativistic effects. The novel relPBE functional serves as an actinide-fitted version of the PBE0 functional, offering an alternative computational approach.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Adam Grofe, Jiali Gao, Xiaosong Li
Summary: The article discusses the extension of the generalized block-localized wave function technique to a relativistic two-component framework and tests the natural symmetry results from Delta SCF optimization. Optimization of excited state determinants for two-component wave functions poses unique challenges due to dense excited state manifolds with degenerate states. Maintaining time-reversal symmetry appears to be roughly achieved with Hartree-Fock, but less so with Kohn-Sham density functional theory, while maintaining total angular momentum symmetry is system dependent and not guaranteed.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Jeremy P. Coe
Summary: We develop analytic gradients for selected configuration interaction wave functions, showing that degenerate orbital pairs belonging to different irreducible representations in the largest abelian subgroup do not need to be included and instabilities due to degeneracies are avoided. We introduce seminumerical gradients and use them to validate the analytic approach even when near degeneracies are present. The method is applied to various molecules, demonstrating the high-quality and efficiency of the analytic gradients for selected configuration interaction.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Viktoria Drontschenko, Daniel Graf, Henryk Laqua, Christian Ochsenfeld
Summary: A method for evaluating analytical frozen-core gradients within the random phase approximation is presented. The method outlines an efficient way to evaluate the response of the density of active electrons and the response of the standard Kohn-Sham density. By using Cholesky decomposed densities, the method achieves speedups in calculations and shows that the errors introduced by the frozen-core approximation are practically insignificant for molecular geometries.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Lorenzo Dona, Jan Gerit Brandenburg, Bartolomeo Civalleri
Summary: The chemical versatility and modular nature of Metal-Organic Frameworks (MOFs) make them unique hybrid inorganic-organic materials for several important applications. The recently proposed sol-3c methods, which combine hybrid functionals and basis set superposition error corrections, have been successfully used to model the structural, vibrational, electronic, and adsorption properties of large MOFs with reasonable computing resources.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Karl Pierce, Edward F. Valeev
Summary: This paper addresses the problem of constructing a canonical polyadic (CP) decomposition for a tensor network rather than a single tensor. It demonstrates how leveraging the structure of the network during CP factor optimization can reduce the complexity of constructing an approximate CP representation. The utility of this technique is shown for approximating the order-4 Coulomb interaction tensor with two order-3 tensors using an approximate generalized square-root (SQ) factorization.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Edward G. Hohenstein, Oumarou Oumarou, Rachael Al-Saadon, Gian-Luca R. Anselmetti, Maximilian Scheurer, Christian Gogolin, Robert M. Parrish
Summary: We propose a Lagrangian-based approach to evaluate relaxed one- and two-particle reduced density matrices from double factorized Hamiltonians, which improves efficiency in computing nuclear gradient and derivative properties.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Hakon Emil Kristiansen, Benedicte Sverdrup Ofstad, Eirill Hauge, Einar Aurbakken, Oyvind Sigmundson Schoyen, Simen Kvaal, Thomas Bondo Pedersen
Summary: In this study, we derive real-time (RT) time and its biorthogonal companion from the time-dependent bivariational principle and a parametrization based on the exponential orbital rotation operator formulation. Applying the TDOMP2 method, we find that absorption spectra are of similar quality to TDCC2 spectra, while frequency-dependent polarizabilities and hyperpolarizabilities are significantly closer to TDCCSD results compared to TDCC2 simulations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
L. Adamowicz, S. Kvaal, C. Lasser, T. B. Pedersen
Summary: This research demonstrates the emergence of alignment from non-BO quantum dynamics simulations and extracts the degree of alignment using pseudo-proton coordinates. The study utilizes time-independent explicitly correlated Gaussian basis functions and a variational, electric-field-dependent basis-set construction procedure.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Correction
Chemistry, Physical
Hakon Emil Kristiansen, Benedicte Sverdrup Ofstad, Eirill Hauge, Einar Aurbakken, Oyvind Sigmundson Schoyen, Simen Kvaal, Thomas Bondo Pedersen
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Medicinal
Daniel Sethio, Vasanthanathan Poongavanam, Ruisheng Xiong, Mohit Tyagi, Duc Duy Vo, Roland Lindh, Jan Kihlberg
Summary: Conformational analysis is crucial for the design of bioactive molecules, and it becomes even more challenging for macrocycles due to their unique characteristics. In this study, we simulated the conformations of five designed macrocycles and verified the results against experimental measurements. Our simulations accurately predicted the intramolecular interactions and revealed a solvent-induced conformational switch of the macrocyclic ring. This provides a foundation for the rational design of molecular chameleons that can adapt to different environments.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Chemistry, Physical
Benedicte Sverdrup Ofstad, Hakon Emil Kristiansen, Einar Aurbakken, Oyvind Sigmundson Schoyen, Simen Kvaal, Thomas Bondo Pedersen
Summary: Real-time simulations of laser-driven electron dynamics allow for the extraction of molecular optical properties through all orders in response theory. However, accuracy deteriorates for higher-order responses due to nonadiabatic effects caused by the finite-time ramping of the external laser field. Three different approaches for extracting electrical properties from real-time electronic-structure simulations are investigated. Quadratic ramping is found to yield highly accurate results at approximately half the computational cost for polarizabilities, hyperpolarizabilities, and a measure of reliability.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Ignacio Fdez Galvan, Roland Lindh
Summary: In this study, a pseudodiabatic surrogate model is developed based on Gaussian process regression, which accurately reproduces the adiabatic surfaces and significantly reduces the computational effort required to obtain minimum energy crossing points using the restricted variance optimization method.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Andy Kaiser, Razan E. Daoud, Francesco Aquilante, Oliver Kuhn, Luca De Vico, Sergey I. Bokarev
Summary: We implemented the Frenkel exciton model into the OpenMolcas program package to calculate collective electronic excited states of molecular aggregates. Our protocol does not rely on diabatization schemes or supermolecule calculations, and the use of Cholesky decomposition for pair interactions improves computational efficiency. We applied our method to two test systems and compared it with the dipole approximation.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Giovanni Li Manni, Ignacio Fdez. Galvan, Ali Alavi, Flavia Aleotti, Francesco Aquilante, Jochen Autschbach, Davide Avagliano, Alberto Baiardi, Jie J. Bao, Stefano Battaglia, Letitia Birnoschi, Alejandro Blanco-Gonzalez, Sergey I. Bokarev, Ria Broer, Roberto Cacciari, Paul B. Calio, Rebecca K. Carlson, Rafael Carvalho Couto, Luis Cerdan, Liviu F. Chibotaru, Nicholas F. Chilton, Jonathan Richard Church, Irene Conti, Sonia Coriani, Juliana Cuellar-Zuquin, Razan E. Daoud, Nike Dattani, Piero Decleva, Coen de Graaf, Mickael G. Delcey, Luca De Vico, Werner Dobrautz, Sijia S. Dong, Rulin Feng, Nicolas Ferre, Michael Filatov (Gulak), Laura Gagliardi, Marco Garavelli, Leticia Gonzalez, Yafu Guan, Meiyuan Guo, Matthew R. Hennefarth, Matthew R. Hermes, Chad E. Hoyer, Miquel Huix-Rotllant, Vishal Kumar Jaiswal, Andy Kaiser, Danil S. Kaliakin, Marjan Khamesian, Daniel S. King, Vladislav Kochetov, Marek Krosnicki, Arpit Arun Kumaar, Ernst D. Larsson, Susi Lehtola, Marie-Bernadette Lepetit, Hans Lischka, Pablo Lopez Rios, Marcus Lundberg, Dongxia Ma, Sebastian Mai, Philipp Marquetand, Isabella C. D. Merritt, Francesco Montorsi, Maximilian Morchen, Artur Nenov, Vu Ha Anh Nguyen, Yoshio Nishimoto, Meagan S. Oakley, Massimo Olivucci, Markus Oppel, Daniele Padula, Riddhish Pandharkar, Quan Manh Phung, Felix Plasser, Gerardo Raggi, Elisa Rebolini, Markus Reiher, Ivan Rivalta, Daniel Roca-Sanjuan, Thies Romig, Arta Anushirwan Safari, Aitor Sanchez-Mansilla, Andrew M. Sand, Igor Schapiro, Thais R. Scott, Javier Segarra-Marti, Francesco Segatta, Dumitru-Claudiu Sergentu, Prachi Sharma, Ron Shepard, Yinan Shu, Jakob K. Staab, Tjerk P. Straatsma, Lasse Kragh Sorensen, Bruno Nunes Cabral Tenorio, Donald G. Truhlar, Liviu Ungur, Morgane Vacher, Valera Veryazov, Torben Arne Voss, Oskar Weser, Dihua Wu, Xuchun Yang, David Yarkony, Chen Zhou, J. Patrick Zobel, Roland Lindh
Summary: This article describes the developments of the open-source OpenMolcas chemistry software environment since spring 2020, focusing on the novel functionalities in the stable branch and interfaces with other packages. These developments cover a wide range of topics in computational chemistry and provide an overview of the chemical phenomena and processes that OpenMolcas can address.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Review
Chemistry, Multidisciplinary
Benedicte Sverdrup Ofstad, Einar Aurbakken, Oyvind Sigmundson Schoyen, Hakon Emil Kristiansen, Simen Kvaal, Thomas Bondo Pedersen
Summary: In recent years, there has been growing interest in time-dependent coupled-cluster (TDCC) theory for simulating laser-driven electronic dynamics in atoms and molecules, as well as molecular vibrational dynamics. This review covers different types of single-reference TDCC theory based on orthonormal static, orthonormal time-dependent, or biorthonormal time-dependent spin orbitals. The time-dependent extension of equation-of-motion coupled-cluster theory and various applications of TDCC methods are also discussed, including the calculation of linear absorption spectra, response functions, high harmonic generation spectra, and ionization dynamics. Additionally, the role of TDCC theory in finite-temperature many-body quantum mechanics and other application areas is briefly described.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2023)
Article
Chemistry, Physical
Juliana Cuellar-Zuquin, Ana Julieta Pepino, Ignacio Fdez Galvan, Ivan Rivalta, Francesco Aquilante, Marco Garavelli, Roland Lindh, Javier Segarra-Marti
Summary: We characterized the photochemically relevant conical intersections between different DNA/RNA nucleobases using CASSCF algorithms. Our results show that the size of the active space significantly affects the conical intersection topographies, while the basis set size seems to have a minor effect. We ruled out structural changes as a key factor and highlighted the importance of accurately describing the electronic states involved in these intersections.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Eirill Hauge, Hakon Emil Kristiansen, Lukas Konecny, Marius Kadek, Michal Repisky, Thomas Bondo Pedersen
Summary: We propose a novel function fitting method for approximating the propagation of the time-dependent electric dipole moment from real-time electronic structure calculations. The method achieves arbitrary spectral resolution through extrapolation by fitting shorter dipole trajectories. Numerical testing demonstrates that this fitting method can reproduce high-resolution spectra using short dipole trajectories.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Multidisciplinary
Hannes Kneiding, Ruslan Lukin, Lucas Lang, Simen Reine, Thomas Bondo Pedersen, Riccardo De Bin, David Balcells
Summary: This paper introduces a method for studying transition metal complexes (TMCs) using deep graph learning, which utilizes electronic structure data from natural bond orbital (NBO) analysis and develops a representation called natural quantum graph (NatQG). With this method, the quantum properties of TMCs can be predicted, and the performance is better compared to traditional descriptor-based methods.
Article
Chemistry, Physical
Giovanni Li Manni, Ignacio Fdez. Galvan, Ali Alavi, Flavia Aleotti, Francesco Aquilante, Jochen Autschbach, Davide Avagliano, Alberto Baiardi, Jie J. Bao, Stefano Battaglia, Letitia Birnoschi, Alejandro Blanco-Gonzalez, Sergey I. Bokarev, Ria Broer, Roberto Cacciari, Paul B. Calio, Rebecca K. Carlson, Rafael Carvalho Couto, Luis Cerdan, Liviu F. Chibotaru, Nicholas F. Chilton, Jonathan Richard Church, Irene Conti, Sonia Coriani, Juliana Cuellar-Zuquin, Razan E. Daoud, Nike Dattani, Piero Decleva, Coen de Graaf, Mickael G. Delcey, Luca De Vico, Werner Dobrautz, Sijia S. Dong, Rulin Feng, Nicolas Ferre, Michael Filatov(Gulak), Laura Gagliardi, Marco Garavelli, Leticia Gonzalez, Yafu Guan, Meiyuan Guo, Matthew R. Hennefarth, Matthew R. Hermes, Chad E. Hoyer, Miquel Huix-Rotllant, Vishal Kumar Jaiswal, Andy Kaiser, Danil S. Kaliakin, Marjan Khamesian, Daniel S. King, Vladislav Kochetov, Marek Krosnicki, Arpit Arun Kumaar, Ernst D. Larsson, Susi Lehtola, Marie-Bernadette Lepetit, Hans Lischka, Pablo Lopez Rios, Marcus Lundberg, Dongxia Ma, Sebastian Mai, Philipp Marquetand, Isabella C. D. Merritt, Francesco Montorsi, Maximilian Morchen, Artur Nenov, Vu Ha Anh Nguyen, Yoshio Nishimoto, Meagan S. Oakley, Massimo Olivucci, Markus Oppel, Daniele Padula, Riddhish Pandharkar, Quan Manh Phung, Felix Plasser, Gerardo Raggi, Elisa Rebolini, Markus Reiher, Ivan Rivalta, Daniel Roca-Sanjuan, Thies Romig, Arta Anushirwan Safari, Aitor Sanchez-Mansilla, Andrew M. Sand, Igor Schapiro, Thais R. Scott, Javier Segarra-Marti, Francesco Segatta, Dumitru-Claudiu Sergentu, Prachi Sharma, Ron Shepard, Yinan Shu, Jakob K. Staab, Tjerk P. Straatsma, Lasse Kragh Sorensen, Bruno Nunes Cabral Tenorio, Donald G. Truhlar, Liviu Ungur, Morgane Vacher, Valera Veryazov, Torben Arne Voss, Oskar Weser, Dihua Wu, Xuchun Yang, David Yarkony, Chen Zhou, J. Patrick Zobel, Roland Lindh
Summary: This article describes the recent developments in the open-source chemistry software environment, OpenMolcas, since spring 2020. It focuses on the new functionalities and interfaces with other packages. The article presents various topics in computational chemistry, including electronic structure theory, electronic spectroscopy simulations, molecular structure optimizations, ab initio molecular dynamics, and other new features. Overall, it highlights the capabilities of OpenMolcas in addressing chemical phenomena and processes, making it an attractive platform for advanced atomistic computer simulations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)