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1,430 results on '"Truhlar, Donald G."'

1. Semiclassical Nonadiabatic Molecular Dynamics Using Linearized Pair-Density Functional Theory

Author

Hennefarth, Matthew R., Truhlar, Donald G., and Gagliardi, Laura

Subjects
Physics - Chemical Physics
Abstract

Nonadiabatic molecular dynamics is an effective method for modeling nonradiative decay in electronically excited molecules. Its accuracy depends strongly on the quality of the potential energy surfaces, and its affordability for long direct-dynamic simulations with adequate ensemble averaging depends strongly on the cost of the required electronic structure calculations. Linearized pair-density functional theory (L-PDFT) is a recently developed post-self-consistent field multireference method that can model potential energy surfaces with an accuracy similar to expensive multireference perturbation theories but at a computational cost similar to the underlying multiconfiguration self-consistent field method. Here we integrate the SHARC dynamics and PySCF electronic structure code to utilize L-PDFT for electronically nonadiabatic calculations and use the combined programs to study the photoisomerization reaction of cis-azomethane. We show that L-PDFT is able to successfully simulate the photoisomerization and yields results similar to the more expensive extended multi-state complete active space second-order perturbation theory. This shows that L-PDFT can model internal conversion, and it demonstrates its promise for broader photodynamics applications., Comment: 8 pages, 5 figures

Published
2024

2. Analytic Nuclear Gradients for Complete Active Space Linearized Pair-Density Functional Theory

Author

Hennefarth, Matthew R., Hermes, Matthew R., Truhlar, Donald G., and Gagliardi, Laura

Subjects
Physics - Chemical Physics
Abstract

Accurately modeling photochemical reactions is difficult due to the presence of conical intersections and locally avoided crossings as well as the inherently multiconfigurational character of excited states. As such, one needs a multi-state method that incorporates state interaction in order to accurately model the potential energy surface at all nuclear coordinates. The recently developed linearized pair-density functional theory (L-PDFT) is a multi-state extension of multiconfiguration PDFT, and it has been shown to be a cost-effective post-MCSCF method (as compared to more traditional and expensive multireference many-body perturbation methods or multireference configuration interaction methods) that can accurately model potential energy surfaces in regions of strong nuclear-electronic coupling in addition to accurately predicting Franck-Condon vertical excitations. In this paper, we report the derivation of analytic gradients for L-PDFT and their implementation in the PySCF-forge software, and we illustrate the utility of these gradients for predicting ground- and excited-state equilibrium geometries and adiabatic excitation energies for formaldehyde, s-trans-butadiene, phenol, and cytosine., Comment: 24 pages, 3 figures

Published
2024
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3. High-throughput predictions of metal–organic framework electronic properties: theoretical challenges, graph neural networks, and data exploration

Author

Rosen, Andrew S, Fung, Victor, Huck, Patrick, O’Donnell, Cody T, Horton, Matthew K, Truhlar, Donald G, Persson, Kristin A, Notestein, Justin M, and Snurr, Randall Q

Subjects
Inorganic Chemistry, Chemical Sciences, Bioengineering, Affordable and Clean Energy, Theoretical and computational chemistry, Materials engineering, Condensed matter physics
Abstract

With the goal of accelerating the design and discovery of metal–organic frameworks (MOFs) for electronic, optoelectronic, and energy storage applications, we present a dataset of predicted electronic structure properties for thousands of MOFs carried out using multiple density functional approximations. Compared to more accurate hybrid functionals, we find that the widely used PBE generalized gradient approximation (GGA) functional severely underpredicts MOF band gaps in a largely systematic manner for semi-conductors and insulators without magnetic character. However, an even larger and less predictable disparity in the band gap prediction is present for MOFs with open-shell 3d transition metal cations. With regards to partial atomic charges, we find that different density functional approximations predict similar charges overall, although hybrid functionals tend to shift electron density away from the metal centers and onto the ligand environments compared to the GGA point of reference. Much more significant differences in partial atomic charges are observed when comparing different charge partitioning schemes. We conclude by using the dataset of computed MOF properties to train machine-learning models that can rapidly predict MOF band gaps for all four density functional approximations considered in this work, paving the way for future high-throughput screening studies. To encourage exploration and reuse of the theoretical calculations presented in this work, the curated data is made publicly available via an interactive and user-friendly web application on the Materials Project.

Published
2022

7. Polyrate 2023: A computer program for the calculation of chemical reaction rates for polyatomics. New version announcement

Author

Meana-Pañeda, Rubén, Zheng, Jingjing, Bao, Junwei Lucas, Zhang, Shuxia, Lynch, Benjamin J., Corchado, José C., Chuang, Yao-Yuan, Fast, Patton L., Hu, Wei-Ping, Liu, Yi-Ping, Lynch, Gillian C., Nguyen, Kiet A., Jackels, Charles F., Fernández-Ramos, Antonio, Ellingson, Benjamin A., Melissas, Vasilios S., Villà, Jordi, Rossi, Ivan, Coitiño, Elena L., Pu, Jingzhi, Albu, Titus V., Zhang, Rui Ming, Xu, Xuefei, Ratkiewicz, Artur, Steckler, Rozeanne, Garrett, Bruce C., Isaacson, Alan D., and Truhlar, Donald G.

Published
2024
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9. Multi-State Pair-Density Functional Theory

Author

Bao, Jie J., Zhou, Chen, Varga, Zoltan, Kanchanakungwankul, Siriluk, Gagliardi, Laura, and Truhlar, Donald G.

Subjects
Physics - Chemical Physics
Abstract

Multiconfiguration pair-density functional theory (MC-PFDT) has previously been applied successfully to carry out ground-state and excited-state calculations. However, because it includes no interaction between electronic states, MC-PDFT calculations can give an unphysical double crossing of potential energy surfaces (PESs) in a region near a conical intersection. We have recently proposed state-interaction pair-density functional theory (SI-PDFT) to treat nearly degenerate states; although this method is successful, it is inconvenient because two SCF calculations and two sets of orbitals are required and because it puts the ground state on an unequal footing with the excited states. Here we propose two new methods, called extended-multi-state-PDFT (XMS-PDFT) and variational-multi-state-PDFT (VMS-PDFT), that generate the intermediate states in a balanced way with a single set of orbitals. The former uses the intermediate states proposed by Granovsky for extended multiconfiguration quasidegenerate perturbation theory (XMC-QDPT); the latter obtains the intermediate states by maximizing the sum of the MC-PDFT energies for the intermediate states. We also propose a Fourier series expansion to make the variational optimizations of the VMS-PDFT method convenient, and we implement this method (FMS-PDFT) both for conventional configuration-interaction solvers and for density-matrix-renormalization-group solvers. The new methods are tested for eight systems exhibiting avoided crossings among two to six states. The FMS-PDFT method is successful for all eight test cases studied in the paper, and XMS-PDFT is successful for all of them except the mixed-valence case. Since both XMS-PDFT and VMS-PDFT are less expensive than XMS-CASPT2, they will allow well-correlated calculations on much larger systems for which perturbation theory is unaffordable.

Published
2020
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15. Density Matrix Renormalization Group Pair-Density Functional Theory (DMRG-PDFT): Singlet-Triplet Gaps in Polyacenes and Polyacetylenes

Author

Sharma, Prachi, Bernales, Varinia, Knecht, Stefan, Truhlar, Donald G., and Gagliardi, Laura

Subjects
Physics - Chemical Physics
Abstract

The density matrix renormalization group (DMRG) is a powerful method to treat static correlation. Here we present an inexpensive way to add additional dynamic correlation energy to a DMRG self-consistent field (DMRG) wave function using pair-density functional theory (PDFT). We applied this new approach, called DMRG-PDFT, to study singlet-triplet gaps in polyacenes and polyacetylenes that require active spaces larger than the feasibility limit of the conventional complete active-space self-consistent field (CASSCF) method. The results match reasonably well the most reliable literature values and have only a moderate dependence on the compression of the initial DMRG wave function. Furthermore, DMRG-PDFT is significantly less expensive than other commonly applied ways of adding additional correlation to DMRG, such as DMRG followed by multireference perturbation theory or multireference configuration interaction.

Published
2018

16. Fluorine-free water-in-ionomer electrolytes for sustainable lithium-ion batteries.

Author

He, Xin, Yan, Bo, Zhang, Xin, Liu, Zigeng, Bresser, Dominic, Wang, Jun, Wang, Rui, Cao, Xia, Su, Yixi, Jia, Hao, Grey, Clare P, Frielinghaus, Henrich, Truhlar, Donald G, Winter, Martin, Li, Jie, and Paillard, Elie

Subjects
MD Multidisciplinary
Abstract

The continuously increasing number and size of lithium-based batteries developed for large-scale applications raise serious environmental concerns. Herein, we address the issues related to electrolyte toxicity and safety by proposing a "water-in-ionomer" type of electrolyte which replaces organic solvents by water and expensive and toxic fluorinated lithium salts by a non-fluorinated, inexpensive and non-toxic superabsorbing ionomer, lithium polyacrylate. Interestingly, the electrochemical stability window of this electrolyte is extended greatly, even for high water contents. Particularly, the gel with 50 wt% ionomer exhibits an electrochemical stability window of 2.6 V vs. platinum and a conductivity of 6.5 mS cm-1 at 20 °C. Structural investigations suggest that the electrolytes locally self-organize and most likely switch local structures with the change of water content, leading to a 50% gel with good conductivity and elastic properties. A LiTi2(PO4)3/LiMn2O4 lithium-ion cell incorporating this electrolyte provided an average discharge voltage > 1.5 V and a specific energy of 77 Wh kg-1, while for an alternative cell chemistry, i.e., TiO2/LiMn2O4, a further enhanced average output voltage of 2.1 V and an initial specific energy of 124.2 Wh kg-1 are achieved.

Published
2018

18. Analytic Gradients for Complete Active Space Pair-Density Functional Theory

Author

Sand, Andrew M., Hoyer, Chad. E., Sharkas, Kamal, Kidder, Katherine M., Lindh, Roland, Truhlar, Donald G., and Gagliardi, Laura

Subjects
Physics - Chemical Physics
Abstract

Analytic gradient routines are a desirable feature for quantum mechanical methods, allowing for efficient determination of equilibrium and transition state structures and several other molecular properties. In this work, we present analytical gradients for multiconfiguration pair-density functional theory (MC-PDFT) when used with a state-specific complete active space self-consistent field reference wave function. Our approach constructs a Lagrangian that is variational in all wave function parameters. We find that MC-PDFT locates equilibrium geometries for several small- to medium-sized organic molecules that are similar to those located by complete active space second-order perturbation theory but that are obtained with decreased computational cost.

Published
2017

20. On the Upper Limits of Oxidation States in Chemistry

Author

Hu, Shu‐Xian, Li, Wan‐Lu, Lu, Jun‐Bo, Bao, Junwei Lucas, Yu, Haoyu S, Truhlar, Donald G, Gibson, John K, Marçalo, Joaquim, Zhou, Mingfei, Riedel, Sebastian, Schwarz, WH Eugen, and Li, Jun

Subjects
Inorganic Chemistry, Chemical Sciences, bonding theory, computational chemistry, oxidation states, oxides, transition metals, Organic Chemistry, Chemical sciences
Abstract

The concept of oxidation state (OS) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum-chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS=+9 was observed for the isolated [IrO4 ]+ cation in vacuum. The prediction of OS=+10 for isolated [PtO4 ]2+ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O-2 with formation of . O-1 and O-O bonds, and partial reduction of the metal center may be favorable, possibly leading to non-Lewis type structures.

Published
2018

21. On the Upper Limits of Oxidation States in Chemistry.

Author

Hu, Shu-Xian, Li, Wan-Lu, Lu, Jun-Bo, Bao, Junwei Lucas, Yu, Haoyu S, Truhlar, Donald G, Gibson, John K, Marçalo, Joaquim, Zhou, Mingfei, Riedel, Sebastian, Schwarz, WH Eugen, and Li, Jun

Subjects
bonding theory, computational chemistry, oxidation states, oxides, transition metals, Organic Chemistry, Chemical Sciences
Abstract

The concept of oxidation state (OS) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum-chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS=+9 was observed for the isolated [IrO4 ]+ cation in vacuum. The prediction of OS=+10 for isolated [PtO4 ]2+ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O-2 with formation of . O-1 and O-O bonds, and partial reduction of the metal center may be favorable, possibly leading to non-Lewis type structures.

Published
2018

27. Dispersion Forces: Neither Fluctuating nor Dispersing

Author

Truhlar, Donald G.

Abstract

Dispersion forces are ubiquitous in chemistry, yet they are often misunderstood. This article provides background into why they are called dispersion forces and explains how to describe them in terms of time-independent quantum mechanics. The article also describes the breakdown of the multipole series that is often used to describe dispersion forces, and it comments on the representation of dispersion forces in molecular mechanics. In general, the article tries to provide a proper framework for understanding and describing dispersion forces.

Published
2019
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29. Quantitative kinetics reveal that reactions of HO2 are a significant sink for aldehydes in the atmosphere and may initiate the formation of highly oxygenated molecules via autoxidation.

Author

Gao, Qiao, Shen, Chuanyang, Zhang, Haofei, Long, Bo, and Truhlar, Donald G.

Abstract

Large aldehydes are widespread in the atmosphere and their oxidation leads to secondary organic aerosols. The current understanding of their chemical transformation processes is limited to hydroxyl radical (OH) oxidation during daytime and nitrate radical (NO3) oxidation during nighttime. Here, we report quantitative kinetics calculations of the reactions of hexanal (C5H11CHO), pentanal (C4H9CHO), and butanal (C3H7CHO) with hydroperoxyl radical (HO2) at atmospheric temperatures and pressures. We find that neither tunneling nor multistructural torsion anharmonicity should be neglected in computing these rate constants; strong anharmonicity at the transition states is also important. We find rate constants for the three reactions in the range 3.2–7.7 × 10−14 cm3 molecule−1 s−1 at 298 K and 1 atm, showing that the HO2 reactions can be competitive with OH and NO3 oxidation under some conditions relevant to the atmosphere. Our findings reveal that HO2-initiated oxidation of large aldehydes may be responsible for the formation of highly oxygenated molecules via autoxidation. We augment the theoretic studies with laboratory flow-tube experiments using an iodide-adduct time-of-flight chemical ionization mass spectrometer to confirm the theoretical predictions of peroxy radicals and the autoxidation pathway. We find that the adduct from HO2 + C5H11CHO undergoes a fast unimolecular 1,7-hydrogen shift with a rate constant of 0.45 s−1. We suggest that the HO2 reactions make significant contributions to the sink of aldehydes. [ABSTRACT FROM AUTHOR]

Published
2024
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32. The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry

Author

Fundación la Caixa, European Commission, Ministerio de Ciencia e Innovación (España), Department of Energy (US), Swiss National Science Foundation, Ministero dell'Istruzione, dell'Università e della Ricerca, Carl Trygger Foundation, Royal Society (UK), Independent Research Fund Denmark, German Research Foundation, Generalitat de Catalunya, Olle Engkvist Foundation, National Centre for Research and Development (Poland), National Science Foundation (US), Academy of Finland, Knut and Alice Wallenberg Foundation, Swedish Research Council, Université de Nantes, Japan Society for the Promotion of Science, Università degli Studi di Siena, Novo Nordisk Foundation, Argonne National Laboratory (US), National University of Singapore, Air Force Office of Scientific Research (US), Linköping University, Centre National de la Recherche Scientifique (France), Li Manni, Giovanni [0000-0002-3666-3880], Fdez Galván, Ignacio [0000-0002-0684-7689], #NODATA#, Aleotti, Flavia [0000-0002-7176-5305], Aquilante, Francesco [0000-0003-4422-3938], Autschbach, Jochen [0000-0001-9392-877X], Avagliano, Davide [0000-0001-5539-9731], Baiardi, Alberto [0000-0001-9112-8664], Bao, Jie J. [0000-0003-0197-3405], Battaglia, Stefano [0000-0002-5082-2681], Blanco-González, Alejandro [0000-0001-7379-2588], Bokarev, Sergey I. [0000-0003-0779-5013], Broer, Ria [0000-0002-5437-9509], Cacciari, Roberto [0000-0001-8290-4297], Calio, Paul B. [0000-0001-8385-2628], Carlson, Rebecca K. [0000-0002-1710-5816], Carvalho Couto, Rafael [0000-0003-4020-0923], Cerdán, L. [0000-0002-7174-2453], Chibotaru, Liviu F. [0000-0003-1556-0812], Chilton, Nicholas F. [0000-0002-8604-0171], Church, Jonathan Richard [0000-0001-5986-1305], Conti, Irene [0000-0001-7982-4480], Coriani, Sonia [0000-0002-4487-897X], Cuéllar-Zuquin, Juliana [0000-0002-0127-579X], Daoud, Razan E. [0000-0001-7034-0770], Dattani, Nike [0000-0001-5667-3632], Decleva, Piero [0000-0002-7322-887X], de Graaf, Coen [0000-0001-8114-6658], Delcey, Mickaël G. [0000-0001-9883-3569], De Vico, Luca [0000-0002-2821-5711], Dobrautz, Werner [0000-0001-6479-1874], Dong, Sijia S. [0000-0001-8182-6522], Feng, Rulin [0000-0002-9812-3804], Ferré, Nicolas [0000-0002-5583-8834], Filatov Gulak, Michael [0000-0002-1541-739X], Gagliardi, Laura [0000-0001-5227-1396], Garavelli, Marco [0000-0002-0796-289X], González, Leticia [0000-0001-5112-794X], Guo, Meiyuan [0000-0003-2474-6264], Hennefarth, Matthew R. [0000-0002-6601-2253], Hermes, Matthew R. [0000-0001-7807-2950], Huix-Rotllant, Miquel [0000-0002-2131-7328], Jaiswal, Vishal Kumar [0000-0002-5090-7984], Kaliakin, Danil S. [0000-0002-9354-8248], King, Daniel S. [0000-0003-0208-5274], Larsson, Ernst D. [0000-0001-7655-2993], Lehtola, Susi [0000-0001-6296-8103], Lepetit, Marie-Bernadette [0000-0001-8730-4282], Lischka, Hans [0000-0002-5656-3975], Lundberg, Marcus [0000-0002-1312-1202], Mai, Sebastian [0000-0001-5327-8880], Marquetand, Philipp [0000-0002-8711-1533], Merritt, Isabella C. D. [0000-0002-7965-7798], Nenov, Artur [0000-0003-3071-5341], Nguyen, Vu Ha Anh [0000-0002-4177-0656], Nishimoto, Yoshio [0000-0001-5581-4712], Oakley, Meagan S. [0000-0001-5072-7572], Olivucci, Massimo [0000-0002-8247-209X], Oppel, Markus [0000-0001-6363-2310], Padula, Daniele [0000-0002-7171-7928], Pandharkar, Riddhish [0000-0003-4086-4308], Phung, Quan Manh [0000-0001-8205-5328], Plasser, Felix [0000-0003-0751-148X], Reiher, Markus [0000-0002-9508-1565], Rivalta, Ivan [0000-0002-1208-602X], Roca-Sanjuán, Daniel [0000-0001-6495-2770], Romig, Thies [0000-0002-9424-2398], Safari, Arta Anushirwan [0000-0003-4511-8902], Sánchez-Mansilla, Aitor [0000-0002-2601-190X], Sand, Andrew M. [0000-0002-7166-2066], Schapiro, Igor [0000-0001-8536-6869], Scott, Thais R. [0000-0002-5746-5517], Segarra-Martí, Javier [0000-0002-2076-3406], Segatta, Francesco [0000-0003-4150-6676], Sergentu, Dumitru-Claudiu [0000-0001-6570-5245], Shepard, Ron [0000-0002-0272-0824], Shu, Yinan [0000-0002-8371-0221], Sørensen, Lasse Kragh [0000-0002-1931-1867], Tenorio, Bruno Nunes Cabral [0000-0002-9702-998X], Truhlar, Donald G. [0000-0002-7742-7294], Ungur, Liviu [0000-0001-5015-4225], Vacher, Morgane [0000-0001-9418-6579], Veryazov, Valera [0000-0002-0172-7047], Li Manni, Giovanni, Fdez Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-González, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Carvalho Couto, Rafael, Cerdán, L., Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuéllar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickaël G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferré, Nicolas, Filatov Gulak, Michael, Gagliardi, Laura, Garavelli, Marco, González, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krośnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie-Bernadette, Lischka, Hans, López Ríos, Pablo, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C. D., Montorsi, Francesco, Mörchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuán, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sánchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Martí, Javier, Segatta, Francesco, Sergentu, Dumitru-Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sørensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voß, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J Patrick, Lindh, Roland, Fundación la Caixa, European Commission, Ministerio de Ciencia e Innovación (España), Department of Energy (US), Swiss National Science Foundation, Ministero dell'Istruzione, dell'Università e della Ricerca, Carl Trygger Foundation, Royal Society (UK), Independent Research Fund Denmark, German Research Foundation, Generalitat de Catalunya, Olle Engkvist Foundation, National Centre for Research and Development (Poland), National Science Foundation (US), Academy of Finland, Knut and Alice Wallenberg Foundation, Swedish Research Council, Université de Nantes, Japan Society for the Promotion of Science, Università degli Studi di Siena, Novo Nordisk Foundation, Argonne National Laboratory (US), National University of Singapore, Air Force Office of Scientific Research (US), Linköping University, Centre National de la Recherche Scientifique (France), Li Manni, Giovanni [0000-0002-3666-3880], Fdez Galván, Ignacio [0000-0002-0684-7689], #NODATA#, Aleotti, Flavia [0000-0002-7176-5305], Aquilante, Francesco [0000-0003-4422-3938], Autschbach, Jochen [0000-0001-9392-877X], Avagliano, Davide [0000-0001-5539-9731], Baiardi, Alberto [0000-0001-9112-8664], Bao, Jie J. [0000-0003-0197-3405], Battaglia, Stefano [0000-0002-5082-2681], Blanco-González, Alejandro [0000-0001-7379-2588], Bokarev, Sergey I. [0000-0003-0779-5013], Broer, Ria [0000-0002-5437-9509], Cacciari, Roberto [0000-0001-8290-4297], Calio, Paul B. [0000-0001-8385-2628], Carlson, Rebecca K. [0000-0002-1710-5816], Carvalho Couto, Rafael [0000-0003-4020-0923], Cerdán, L. [0000-0002-7174-2453], Chibotaru, Liviu F. [0000-0003-1556-0812], Chilton, Nicholas F. [0000-0002-8604-0171], Church, Jonathan Richard [0000-0001-5986-1305], Conti, Irene [0000-0001-7982-4480], Coriani, Sonia [0000-0002-4487-897X], Cuéllar-Zuquin, Juliana [0000-0002-0127-579X], Daoud, Razan E. [0000-0001-7034-0770], Dattani, Nike [0000-0001-5667-3632], Decleva, Piero [0000-0002-7322-887X], de Graaf, Coen [0000-0001-8114-6658], Delcey, Mickaël G. [0000-0001-9883-3569], De Vico, Luca [0000-0002-2821-5711], Dobrautz, Werner [0000-0001-6479-1874], Dong, Sijia S. [0000-0001-8182-6522], Feng, Rulin [0000-0002-9812-3804], Ferré, Nicolas [0000-0002-5583-8834], Filatov Gulak, Michael [0000-0002-1541-739X], Gagliardi, Laura [0000-0001-5227-1396], Garavelli, Marco [0000-0002-0796-289X], González, Leticia [0000-0001-5112-794X], Guo, Meiyuan [0000-0003-2474-6264], Hennefarth, Matthew R. [0000-0002-6601-2253], Hermes, Matthew R. [0000-0001-7807-2950], Huix-Rotllant, Miquel [0000-0002-2131-7328], Jaiswal, Vishal Kumar [0000-0002-5090-7984], Kaliakin, Danil S. [0000-0002-9354-8248], King, Daniel S. [0000-0003-0208-5274], Larsson, Ernst D. [0000-0001-7655-2993], Lehtola, Susi [0000-0001-6296-8103], Lepetit, Marie-Bernadette [0000-0001-8730-4282], Lischka, Hans [0000-0002-5656-3975], Lundberg, Marcus [0000-0002-1312-1202], Mai, Sebastian [0000-0001-5327-8880], Marquetand, Philipp [0000-0002-8711-1533], Merritt, Isabella C. D. [0000-0002-7965-7798], Nenov, Artur [0000-0003-3071-5341], Nguyen, Vu Ha Anh [0000-0002-4177-0656], Nishimoto, Yoshio [0000-0001-5581-4712], Oakley, Meagan S. [0000-0001-5072-7572], Olivucci, Massimo [0000-0002-8247-209X], Oppel, Markus [0000-0001-6363-2310], Padula, Daniele [0000-0002-7171-7928], Pandharkar, Riddhish [0000-0003-4086-4308], Phung, Quan Manh [0000-0001-8205-5328], Plasser, Felix [0000-0003-0751-148X], Reiher, Markus [0000-0002-9508-1565], Rivalta, Ivan [0000-0002-1208-602X], Roca-Sanjuán, Daniel [0000-0001-6495-2770], Romig, Thies [0000-0002-9424-2398], Safari, Arta Anushirwan [0000-0003-4511-8902], Sánchez-Mansilla, Aitor [0000-0002-2601-190X], Sand, Andrew M. [0000-0002-7166-2066], Schapiro, Igor [0000-0001-8536-6869], Scott, Thais R. [0000-0002-5746-5517], Segarra-Martí, Javier [0000-0002-2076-3406], Segatta, Francesco [0000-0003-4150-6676], Sergentu, Dumitru-Claudiu [0000-0001-6570-5245], Shepard, Ron [0000-0002-0272-0824], Shu, Yinan [0000-0002-8371-0221], Sørensen, Lasse Kragh [0000-0002-1931-1867], Tenorio, Bruno Nunes Cabral [0000-0002-9702-998X], Truhlar, Donald G. [0000-0002-7742-7294], Ungur, Liviu [0000-0001-5015-4225], Vacher, Morgane [0000-0001-9418-6579], Veryazov, Valera [0000-0002-0172-7047], Li Manni, Giovanni, Fdez Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-González, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Carvalho Couto, Rafael, Cerdán, L., Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuéllar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickaël G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferré, Nicolas, Filatov Gulak, Michael, Gagliardi, Laura, Garavelli, Marco, González, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krośnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie-Bernadette, Lischka, Hans, López Ríos, Pablo, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C. D., Montorsi, Francesco, Mörchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuán, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sánchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Martí, Javier, Segatta, Francesco, Sergentu, Dumitru-Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sørensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voß, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J Patrick, and Lindh, Roland

Abstract

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

Published
2023

39. Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)–Oxo Sites in Magnesium-Diluted Fe2(dobdc)

Author

Verma, Pragya, Vogiatzis, Konstantinos D, Planas, Nora, Borycz, Joshua, Xiao, Dianne J, Long, Jeffrey R, Gagliardi, Laura, and Truhlar, Donald G

Subjects
Binding Sites, Catalysis, Coordination Complexes, Ethane, Ethanol, Iron Compounds, Magnesium, Models, Molecular, Oxidation-Reduction, Oxygen, Quantum Theory, Chemical Sciences, General Chemistry
Abstract

The catalytic properties of the metal-organic framework Fe2(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe2(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)-oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and nonheme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe0.1Mg1.9(dobdc), activates the strong C-H bonds of ethane. Kohn-Sham density functional and multireference wave function calculations have been performed to characterize the electronic structure of key species. We show that the catalytic nonheme-Fe hydroxylation of the strong C-H bond of ethane proceeds by a quintet single-state σ-attack pathway after the formation of highly reactive iron-oxo intermediate. The mechanistic pathway involves three key transition states, with the highest activation barrier for the transfer of oxygen from N2O to the Fe(II) center. The uncatalyzed reaction, where nitrous oxide directly oxidizes ethane to ethanol is found to have an activation barrier of 280 kJ/mol, in contrast to 82 kJ/mol for the slowest step in the iron(IV)-oxo catalytic mechanism. The energetics of the C-H bond activation steps of ethane and methane are also compared. Dehydrogenation and dissociation pathways that can compete with the formation of ethanol were shown to involve higher barriers than the hydroxylation pathway.

Published
2015

47. Polyrate 2023:A Computer Program for the Calculation of Chemical Reaction Rates for Polyatomics. New Version Announcement

Author

Meana-Pañeda, Rubén, primary, Zheng, Jingjing, additional, Bao, Junwei Lucas, additional, Zhang, Shuxia, additional, Lynch, Benjamin J., additional, Corchado, José C., additional, Chuang, Yao-Yuan, additional, Fast, Patton L., additional, Hu, Wei-Ping, additional, Liu, Yi-Ping, additional, Lynch, Gillian C., additional, Nguyen, Kiet A., additional, Jackels, Charles F., additional, Fernández-Ramos, Antonio, additional, Ellingson, Benjamin A., additional, Melissas, Vasilios S., additional, Villà, Jordi, additional, Rossi, Ivan, additional, Coitiño, Elena L., additional, Pu, Jingzhi, additional, Albu, Titus V., additional, Zhang, Rui Ming, additional, Xu, Xuefei, additional, Ratkiewicz, Artur, additional, Steckler, Rozeanne, additional, Garrett, Bruce C., additional, Isaacson, Alan D., additional, and Truhlar, Donald G., additional

Published
2023
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