Article
Chemistry, Physical
Abhishek Mitra, Hung Q. Pham, Riddhish Pandharkar, Matthew R. Hermes, Laura Gagliardi
Summary: The study explores the application of embedding-based methods in electronic excitations of solid-state defects, showing that the DMET method can achieve high accuracy. The practicality of the method is extended and validated in oxygen vacancies on the MgO(100) surface and neutral silicon vacancies in diamond.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Gabriel L. S. Rodrigues, Mikael Scott, Mickael G. Delcey
Summary: Multiconfigurational pair-density functional theory (MC-PDFT) is an inexpensive way to describe both strong and dynamic correlations. This study demonstrates that the previously neglected imaginary component is actually necessary to reproduce the correct physical behavior, especially in low-spin open shell systems.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Juan Carlos Roldao, Eliezer Fernando Oliveira, Begona Milian-Medina, Johannes Gierschner, Daniel Roca-Sanjuan
Summary: This study investigates the calculation of excited-state absorption spectra using QR TD-DFT and CASPT2 for oligophenylenevinylenes and oligothiophenes. CASPT2 provides a reliable description of the spectra, while QR TD-DFT gives reasonable results under certain conditions. The failure of QR TD-DFT is attributed to incomplete configuration description and improper MO description.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Materials Science, Multidisciplinary
Churna Bhandari, Aleksander L. Wysocki, Sophia E. Economou, Pratibha Dev, Kyungwha Park
Summary: Research has shown that multiconfigurational quantum chemistry methods accurately describe the electronic states of deep defects in wide band gap semiconductors, providing good predictive capabilities for their properties. Using the NV- center as a prototype, the study successfully revealed the many-body characteristics of the defect center by properly considering electron correlations and spin coupling in quantum chemistry calculations.
Article
Physics, Particles & Fields
Oliver Baer, Alexander Broll, Rainer Sommer
Summary: This study uses heavy meson chiral perturbation theory to estimate the contamination effects caused by additional pions in lattice simulations. The results show that these contamination effects generally lead to an overestimation of B meson observables.
EUROPEAN PHYSICAL JOURNAL C
(2023)
Article
Optics
V. N. Glushkov
Summary: The possibilities of using distributive bases from Gaussian sp-functions for calculating the correlation energy of molecules in the second order of the Moller-Plesset perturbation theory have been investigated. The effectiveness of such bases has been demonstrated by comparing the values obtained in distributive and standard atom-centered bases, showing that distributive sp-functions provide accuracy comparable to atom-centered bases. This study also developed an analog of Moller-Plesset perturbation theory for excited states while preserving its advantages for ground states.
OPTICS AND SPECTROSCOPY
(2021)
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
John Mark P. Martirez, Emily A. Carter
Summary: The combination of DFT and CW theory accurately simulates absorption spectra and excited-state properties in dye-sensitized solar cells, providing efficient predictions of metal-to-ligand charge-transfer excited properties. The use of an embedding potential that describes the interaction between the molecule and the TiO2 cluster allows for precise predictions of local properties at a manageable computational cost. This approach can lead to improved understanding of excited-state processes and potentially enhance charge separation efficiency in solar cells.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Katarzyna Pernal, Michal Hapka
Summary: Range-separated multiconfigurational density functional theory (RS MC-DFT) combines density functional and wavefunction theories by partitioning the electron interaction operator and modeling with different methods. RS MC-DFT aims to increase versatility and accuracy of methods while reducing computational cost. Variants of RS MC-DFT can be divided into single-determinant-based and multideterminantal approaches for describing electron correlation energy. Applications include ground-state properties of molecules and noncovalent interactions, as well as time-dependent linear-response theory and direct approaches to excited states. Advantages of RS MC-DFT over conventional DFT and ab initio methods are assessed for each area of application.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2022)
Article
Chemistry, Physical
Woojin Park, Seunghoon Lee, Miquel Huix-Rotllant, Michael Filatov, Cheol Ho Choi
Summary: In this study, the non-radiative relaxation mechanism of photoexcited thymine in the gas phase was investigated using non-adiabatic molecular dynamics simulations. The results support the S-1-trapping mechanism and are quantitatively consistent with recent experiments.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Adam Grofe, Ruoqi Zhao, Andrew Wildman, Torin F. Stetina, Xiaosong Li, Peng Bao, Jiali Gao
Summary: The generalized block-localized orbital (GBLO) method described in this article offers insights on chemical bonding and intermolecular interactions through constrained orbitals. It allows for convenient optimization tailored by specific constraints, significantly reducing computational errors.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Ke Liao, Huanchen Zhai, Evelin Martine Christlmaier, Thomas Schraivogel, Pablo Lopez Rios, Daniel Kats, Ali Alavi
Summary: We present a theory for a DMRG algorithm that can solve for both the ground and excited states of non-Hermitian transcorrelated Hamiltonians and demonstrate its applications in molecular systems. The method involves including known physics in the Jastrow factor to accelerate the basis set convergence rate. By making minimal changes to the existing TI-DMRG algorithm, we are able to efficiently find the ground and excited states with improved accuracy compared to the original DMRG method.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Jan-Niklas Boyn, Aleksandr O. Lykhin, Scott E. Smart, Laura Gagliardi, David A. Mazziotti
Summary: Hybrid quantum-classical algorithms offer a promising pathway to achieve quantum advantage by leveraging both quantum and classical computing resources. A novel combination of quantum and classical algorithms has been developed to compute the energy of strongly correlated molecular systems with experimental accuracy on noisy intermediate-scale quantum devices, demonstrating chemically relevant and accurate results.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Christopher J. N. Coveney, David P. P. Tew
Summary: We propose a scalable single-particle framework for treating electronic correlation in molecules and materials based on Green's function theory. By introducing the Goldstone self-energy, we derive a size-extensive Brillouin-Wigner perturbation theory from the single-particle Green's function. This new ground state correlation energy, named Quasi-Particle MP2 theory (QPMP2), avoids the characteristic divergences in strongly correlated systems present in second-order Moller-Plesset perturbation theory and Coupled Cluster Singles and Doubles methods, and demonstrates excellent performance in reproducing exact ground state energy and properties of the Hubbard dimer as well as larger Hubbard models.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Daniel S. King, Donald G. Truhlar, Laura Gagliardi
Summary: MC-DDFMs are methods aiming to correct the energy of multiconfigurational wave functions using a machine-learned functional of some wave function feature, such as density or on-top density. These methods show promise for the development of MC-PDFT functionals and are able to achieve near-benchmark performance on systems not used for training, indicating a degree of active-space independence.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Javier Carmona-Garcia, Antonio Frances-Monerris, Carlos A. Cuevas, Tarek Trabelsi, Alfonso Saiz-Lopez, Joseph S. Francisco, Daniel Roca-Sanjuan
Summary: This study investigates the photochemical behavior of hydroxysulfinyl radical, revealing that its major solar-induced channel is photocleavage to HO + SO, with a minor contribution of H + SO2 photoproducts. The efficient generation of SO is relevant due to its reactivity with O(3) and subsequent depletion of ozone in the stratosphere.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Juan Carlos Roldao, Eliezer Fernando Oliveira, Begona Milian-Medina, Johannes Gierschner, Daniel Roca-Sanjuan
Summary: State-of-the-art CASPT2 calculations are used to investigate the effect of double excitations on the GSA and ESA spectra of distyrylbenzene. The multi-reference results provide a more accurate description of electronic transitions compared to DFT results. Careful selection of the active space and basis set in the CASPT2 approach allows for a reliable description of spectral features, with cost-effective DFT-based geometries being applicable without significant loss of accuracy. Double excitations play a crucial role in higher excited states in the GSA spectrum, but have minimal impact on discernible spectral features. In the more complex ESA, a multiconfigurational treatment with double (and higher) excitations is essential.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Francesc Bejarano, Diego Gutierrez, Jose Catalan-Toledo, Daniel Roca-Sanjuan, Johannes Gierschner, Jaume Veciana, Marta Mas-Torrent, Concepcio Rovira, Nuria Crivillers
Summary: This study investigates the photoisomerization of an asymmetrically substituted styrene containing a redox-active ferrocene moiety and a terminal alkyne group in solution, and upon forming chemisorbed self-assembled monolayers. The charge transport measurements across the monolayers show that there is an alteration of the isomerization pathway when linked to the gold substrate, favoring trans to cis conversion compared to solution. The experimental results are interpreted based on quantum chemistry calculations.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Correction
Multidisciplinary Sciences
Alfonso Saiz-Lopez, Sebastian P. Sitkiewicz, Daniel Roca-Sanjuan, Josep M. Oliva-Enrich, Juan Z. Davalos, Rafael Notario, Martin Jiskra, Yang Xu, Feiyue Wang, Colin P. Thackray, Elsie M. Sunderland, Daniel J. Jacob, Oleg Travnikov, Carlos A. Cuevas, A. Ulises Acuna, Daniel Rivero, John M. C. Plane, Douglas E. Kinnison, Jeroen E. Sonke
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Luis Cerdan, Daniel Roca-Sanjuan
Summary: The theoretical prediction of molecular electronic spectra is important for understanding various photophysical and photochemical processes. The Nuclear Ensemble Approach (NEA) is a popular computational strategy, but it has limitations in selecting the broadening parameter and dealing with outliers. In this study, we propose a new approach called GMM-NEA, which uses Gaussian Mixture Models to reconstruct spectra and detect anomalous computations. Our results show that GMM-NEA outperforms other data-driven models in selecting the broadening parameter for small datasets.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Bo Long, Yu Xia, Junwei Lucas Bao, Javier Carmona-Garcia, Juan Carlos Gomez Martin, John M. C. Plane, Alfonso Saiz-Lopez, Daniel Roca-Sanjuan, Joseph S. Francisco
Summary: Sulfur trioxide (SO3) plays a critical role in the sulfur cycle and the formation of sulfuric acid in the atmosphere. The traditional understanding is that SO3 is removed by water vapor in the troposphere, but this study reveals that at higher altitudes where water vapor concentration decreases, the atmospheric lifetime of SO3 is extended. The findings suggest that the reaction of SO3 with nitric acid (HONO2) could potentially act as a removal reaction for both SO3 in the stratosphere and HONO2 in the troposphere. This study also uncovers an unexpected new product from the reaction between SO3 and HONO2, which has implications for understanding sulfur partitioning in the stratosphere.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Geosciences, Multidisciplinary
Alfonso Saiz-Lopez, A. Ulises Acuna, Anoop S. Mahajan, Juan Z. Davalos, Wuhu Feng, Daniel Roca-Sanjuan, Javier Carmona-Garcia, Carlos A. Cuevas, Douglas E. Kinnison, Juan Carlos Gomez Martin, Joseph S. Francisco, John M. C. Plane
Summary: This article presents the first model of stratospheric mercury chemistry and identifies two distinct mercury chemical regimes. The study also reveals that the oxidation of mercury in the stratosphere is faster than previously assumed, but regulated by photo-reduction. The lifetime of mercury in the stratosphere shows a significant variation.
GEOPHYSICAL RESEARCH LETTERS
(2022)
Article
Chemistry, Physical
Juan Carlos Roldao, Eliezer Fernando Oliveira, Begona Milian-Medina, Johannes Gierschner, Daniel Roca-Sanjuan
Summary: This study investigates the calculation of excited-state absorption spectra using QR TD-DFT and CASPT2 for oligophenylenevinylenes and oligothiophenes. CASPT2 provides a reliable description of the spectra, while QR TD-DFT gives reasonable results under certain conditions. The failure of QR TD-DFT is attributed to incomplete configuration description and improper MO description.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Multidisciplinary Sciences
Antonio Frances-Monerris, Javier Carmona-Garcia, Tarek Trabelsi, Alfonso Saiz-Lopez, James R. Lyons, Joseph S. Francisco, Daniel Roca-Sanjuan
Summary: This study presents a novel mechanism for the formation of polysulfur compounds in the atmosphere of Venus, demonstrating the production of S-2 and filling critical data gaps.
NATURE COMMUNICATIONS
(2022)
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)
Article
Multidisciplinary Sciences
Yee Jun Tham, Nina Sarnela, Siddharth Iyer, Qinyi Li, Helene Angot, Lauriane L. J. Quelever, Ivo Beck, Tiia Laurila, Lisa J. Beck, Matthew Boyer, Javier Carmona-Garcia, Ana Borrego-Sanchez, Daniel Roca-Sanjuan, Otso Perakyla, Roseline C. Thakur, Xu-Cheng He, Qiaozhi Zha, Dean Howard, Byron Blomquist, Stephen D. Archer, Ludovic Bariteau, Kevin Posman, Jacques Hueber, Detlev Helmig, Hans-Werner Jacobi, Heikki Junninen, Markku Kulmala, Anoop S. Mahajan, Andreas Massling, Henrik Skov, Mikko Sipila, Joseph S. Francisco, Julia Schmale, Tuija Jokinen, Alfonso Saiz-Lopez
Summary: Observations report the presence of HClO3 and HClO4 in the atmosphere, showing their widespread occurrence over the pan-Arctic during spring. These findings provide further insights into atmospheric chlorine cycling in the polar environment. The increase in HClO3 and HClO4 is linked to the increase in bromine levels, indicating the role of bromine chemistry in their formation and suggesting a previously missing atmospheric sink for reactive chlorine.
NATURE COMMUNICATIONS
(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, Organic
Gemma M. Rodriguez-Muniz, Ana B. Fraga-Timiraos, Miriam Navarrete-Miguel, Ana Borrego-Sanchez, Daniel Roca-Sanjuan, Miguel A. Miranda, Virginie Lhiaubet-Vallet
Summary: The desire to achieve simple systems that can photoreductively split four-membered ring compounds is of interest in both inorganic chemistry and biochemistry, with the aim to mimic the activity of DNA photorepair enzymes. In this study, dyads containing the cyclobutane thymine dimer and guanine or 8-oxoguanine are synthesized, and their photoreactivities are compared. The results show that both dyads can split the ring, resulting in the formation of thymine, but with a lower quantum yield for the guanine derivative.
JOURNAL OF ORGANIC CHEMISTRY
(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 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)