Article
Chemistry, Inorganic & Nuclear
Qi-Feng Gao, Tan-Lin Jiang, Wei-Zhou Li, Deng-Feng Tan, Xiu-Hai Zhang, Jin-Ying Pang, Shu-Hua Zhang
Summary: Two highly stable Zn(II) metal-organic frameworks (MOFs), [Zn2(L)2(HIPA)]n (1) and [Zn9(L)6(BTEC)3(H2O)4 center dot 6H2O]n (2) (L = 3-amino-1H-1,2,4-triazole, HIPA = 5-hydroxyisophthalic acid, BTEC = benzene-1,2,4,5-tetracarboxylic acid), were synthesized using a hydrothermal method. The physicochemical properties of the MOFs were characterized, and their stability was confirmed under heating. The MOFs were then used as catalysts in a grafting reaction, showing higher grafting efficiency compared to other catalysts.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Fernando D. Vila, John J. Rehr, Himadri Pathak, Bo Peng, Ajay Panyala, Erdal Mutlu, Nicholas P. Bauman, Karol Kowalski
Summary: The newly developed coupled-cluster methods are effective in simulating ionization potentials and spectral functions of molecular systems. Different methods compared in this paper show good agreement with each other and with experimental results.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
John F. Stanton
Summary: The study investigates the marked anharmonicity of the CC stretching mode in the ethynyl radical using a vibronic coupling model, attributing the large difference between the harmonic frequency and the fundamental level to vibronic interaction between electronic states. The profound vibronic influence due to strong tuning of gap energy by the CC stretch mode is highlighted, emphasizing the advantage of equation-of-motion CC methods for calculations.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Inorganic & Nuclear
Linda Zhang, Toshiki Wulf, Florian Baum, Wolfgang Schmidt, Thomas Heine, Michael Hirscher
Summary: In this study, ion-exchanged zeolite has been reported as a promising candidate for hydrogen isotope separation. Through systematic investigation, it has been found that the Ag(I)-exchanged zeolite Y exhibits excellent selectivity and adsorption performance, making it suitable for large-scale applications.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Monika Kodrycka, Konrad Patkowski
Summary: This study improves the convergence performance of dispersion and exchange-dispersion corrections in symmetry-adapted perturbation theory by decomposing all types of two-electron integrals using robust density fitting. The new implementation demonstrates improved basis set convergence and computational efficiency, allowing for accurate calculations of total SAPT interaction energies at different levels. Additionally, the F12 treatment substantially enhances the accuracy of small-basis calculations in high-level SAPT approaches when theory errors are minimized.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Weitang Li, Jonathan Allcock, Lixue Cheng, Shi-Xin Zhang, Yu-Qin Chen, Jonathan P. Mailoa, Zhigang Shuai, Shengyu Zhang
Summary: TenCirChem is an open-source Python library that simulates variational quantum algorithms for quantum computational chemistry. It performs well in simulating unitary coupled-cluster circuits, using compact representations of quantum states and excitation operators. TenCirChem also supports noisy circuit simulation and provides algorithms for variational quantum dynamics. It demonstrates its capabilities through various examples and is capable of running real quantum hardware experiments, making it a versatile tool for simulation and experimentation in quantum computational chemistry.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Ilya G. Ryabinkin, Andrew J. Jena, Scott N. Genin
Summary: We propose an efficient method for constructing a fully anticommutative set of Pauli generators from a commutative set of operators composed exclusively of purely X generators. The method involves using Gauss-Jordan elimination on a binary matrix encoding the X generators to reduce it to row-echelon form, followed by a modified Jordan-Wigner transformation to construct an anticommutative system in a standard basis. The resulting anticommutative sets are then used for the qubit coupled cluster Ansatz and applied to calculations of ground-state potential energy curves for molecular systems.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Medicinal
Paul L. Turtscher, Markus Reiher
Summary: This study introduces a graph-optimization-driven algorithm and program called PATHFINDER for analyzing chemical reaction networks (CRNs). The CRN is represented as a graph, with compounds and reactions as vertices and activation barriers and required reagents as edges. Compound costs are introduced to reflect availability, and compounds are ranked based on their probability of formation. PATHFINDER is demonstrated in the analysis of an abstract CRN and the disproportionation of iodine with water and comproportionation of iodic acid and hydrogen iodide.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Chemistry, Physical
Jiguang Li, Da Lei, Zhiwei Ma, Baiyi Zu, Xincun Dou
Summary: The exploration of organic fluorescent sensing materials and mechanisms, especially for the deep understanding of twisted intramolecular charge transfer (TICT), is of great significance. In this study, the electron-donating ability of a chemically protonated amino group and the corresponding excitation were found to ensure the occurrence of excited-state intramolecular proton transfer. The hybridization of the amino group and the steric hindrance effect and conjugative effect contribute to the rotation efficiency of the TICT process and the elimination of the background fluorescent signal. The detection of trace nitrite particulate was achieved, and the protonation-induced change in the amino group configuration was verified. These findings are expected to facilitate the exploration of novel fluorescent sensing mechanisms.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Magdalena Woinska, Michal L. Chodkiewicz, Krzysztof Wozniak
Summary: A comparison of five X-ray structures of transition-metal-bound hydride complexes, refined using Hirshfeld Atom Refinement (HAR), shows that using aspherical atomic scattering factors results in systematic elongation of metal-hydrogen bonds. This leads to excellent agreement between X-ray and neutron-derived bond lengths in cases of highest-quality data.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Depeng Li, Qingqing Guan, Xiaoyun Hu, Yuhong Su, Zhen Su
Summary: A new simple Pt(ii) terpyridyl salt that shows reversible response towards acetonitrile and irreversible response towards methanol has been reported, accompanied with the colorimetric/luminescent changing from red to yellow. Experimentally and theoretically, the spectroscopic change derives from the hydrogen bonds between crystal water in the Pt(ii) terpyridyl salt and external organic molecules, and the different strength of hydrogen bond leads either reversible or irreversible stimuli-response. Furthermore, this Pt(ii) terpyridyl salt has been on one hand applied as a probe for sensing acetonitrile in water solution, with high selectivity, good reversibility, proper sensitivity and fast response rate, and on the other hand as advanced anticounterfeiting materials. The current study provides a new approach to acquire and design either reversible or irreversible stimuli-responsive luminescent materials.
Article
Chemistry, Physical
Bilel Mehnen, Saida Ben Yaghlane, Piotr Zuchowski, Dariusz Kedziera, Muneerah Mogren Al-Mogren, Majdi Hochlaf
Summary: Using post Hartree-Fock multi-configuration interaction ab initio methods, the electronic states and potential energy surfaces of thioxophosphane cation, HPS+, are studied. The rotational and vibrational constants and rovibrational levels of these states are determined. An accurate adiabatic ionization energy of HPS is also deduced. This research provides useful spectroscopic data for identifying HPS+ in laboratory and in reactive collision media.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Physical
Samragni Banerjee, Tianyuan Zhang, Kenneth G. Dyall, Xiaosong Li
Summary: This study presents an efficient integral decomposition approach for in-core relativistic quantum chemistry calculations. The approach, called the restricted-kinetic-balance resolution-of-the-identity (RKB-RI) algorithm, incorporates the restricted-kinetic-balance condition and offers a versatile framework for accurate computations. The study also investigates crucial conditions, such as kinetic balance and variational stability, and compares the computational cost with the full in-core method.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Muhammad F. Kasim, Susi Lehtola, Sam M. Vinko
Summary: Automatic differentiation is a paradigm shift in scientific programming that simplifies calculations and reduces development time. It has fuelled the growth of machine learning techniques and is also proving valuable in quantum chemistry simulations.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Tamara Husch, Jiace Sun, Lixue Cheng, Sebastian J. R. Lee, Thomas F. Miller
Summary: MOB-ML is a molecular orbital-based machine learning approach that can accurately predict correlation energies. By preserving physical constraints, MOB-ML demonstrates numerical improvements on different datasets. By training on only 1% of the QM7b-T dataset, it can predict the total energy of the remaining 99% with higher accuracy compared to other methods.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Correction
Chemistry, Physical
Wenqi Chen, Pengchao Zhang, Donald G. Truhlar, Jingjing Zheng, Xuefei Xu
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Yinan Shu, Linyao Zhang, Dihua Wu, Xiye Chen, Shaozeng Sun, Donald G. Truhlar
Summary: It is recommended to use the fully adiabatic basis for trajectory surface hopping (TSH) calculations, where the Hamiltonian is diagonal. Traditional TSH methods for simulating intersystem crossing processes require explicit computation of nonadiabatic coupling vectors (NACs) in the molecular-Coulomb-Hamiltonian (MCH) basis, in order to compute the gradient in the fully adiabatic basis. However, this explicit requirement hinders the advantages of overlap-based and curvature-driven algorithms used for efficient TSH calculations. A new computation scheme called the time-derivative-matrix scheme is proposed to circumvent the need for NACs.
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
Chemistry, Physical
Xiaorui Zhao, Yinan Shu, Linyao Zhang, Xuefei Xu, Donald G. Truhlar
Summary: Mixed quantum-classical nonadiabatic dynamics is widely used for simulating molecular dynamics involving multiple electronic states. Trajectory surface hopping (TSH) and self-consistent potential (SCP) methods are the two main categories of such dynamics algorithms. This work illustrates an example of severe population leaking in TSH, which is caused by frustrated hops and long-time simulations driving the excited-state population towards zero over time. The leaking can be partially alleviated by the fewest switches with time uncertainty (TSH) algorithm, but not completely eliminated.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Matthew R. Hennefarth, Matthew R. Hermes, Donald G. Truhlar, Laura Gagliardi
Summary: Multiconfigurationpair-density functional theory (MC-PDFT) is a successful method for computing ground- and excited-state energies. However, it can lead to inaccurate potential energy surfaces near avoided crossings and conical intersections. In order to overcome this limitation and accurately describe molecular dynamics and Jahn-Teller instabilities, a new method called linearized PDFT (L-PDFT) is proposed. L-PDFT effectively recovers the correct potential energy surface topology and outperforms previous methods for predicting vertical excitations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Jiaxin Ning, Donald G. Truhlar
Summary: Using theoretical computations, we studied the photodissociation process of ortho-Fluorothiophenol (o-FTP). We found that the introduction of a fluorine atom in o-FTP leads to the formation of a hydrogen bond with the hydrogen atom of the SH group, which is not commonly observed in other pi sigma* processes. Theoretical calculations are important for studying these reactions as they provide a deeper understanding of the processes compared to current spectroscopic methods.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Aleksandr O. Lykhin, Moritz K. A. Baumgarten, Donald G. Truhlar, Laura Gagliardi
Summary: We develop response-function algorithms for dipole moments and transition dipole moments for compressed multistate pair-density functional theory (CMS-PDFT). We use the method of undetermined Lagrange multipliers to derive analytical expressions and validate them using numerical differentiation. We show that CMS-PDFT has good accuracy for ground-state and excited-state dipole moments, and can provide correct behavior for the dipole moment curves in the vicinity of conical intersections, which opens the door to molecular dynamic simulations in strong electric fields and the discovery of chemical reactions that can be controlled by an oriented external electric field upon photoexcitation of the reactants.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
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
Chemistry, Physical
Daniel S. King, Donald G. Truhlar, Laura Gagliardi
Summary: The selection of active orbitals for modeling strongly correlated electronic states is challenging and highly dependent on the specific states and molecules of interest. The authors propose a discrete variational selection (DVS) approach to tackle this problem by generating multiple trial wave functions from systematically constructed active spaces and choosing the best one variationally. They apply this approach to a database of small-to-medium-sized molecules and find that it performs well in selecting wave functions based on the energy from multiconfiguration pair-density functional theory.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Yinan Shu, Zoltan Varga, Dayou Zhang, Donald G. Truhlar
Summary: Constructing analytic representations of potential energy surfaces is difficult, especially when coupled potential energy surfaces and their nonadiabatic couplings are involved. In order to facilitate the use of developed potentials, we have created ChemPotPy, a user-friendly library for analytic representation of single-state and multistate potential energy surfaces and couplings.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Maryam Mansoori Kermani, Hanwei Li, Alistar Ottochian, Orlando Crescenzi, Benjamin G. Janesko, Giovanni Scalmani, Michael J. Frisch, Ilaria Ciofini, Carlo Adamo, Donald G. Truhlar
Summary: Theoretical characterization of reactions of complex molecules requires accurate determination of the relative energies of intermediates and transition states. In this study, the DLPNO-CCSD(T) method was employed to provide benchmark values for Diels-Alder transition states leading to strained pentacyclic adducts. Various wave function and density functional methods were compared for their prediction of absolute and relative barrier heights. The results show that only a few density functionals can satisfactorily predict absolute barrier heights, while relative barrier heights are more accurate. The findings of this study can guide the selection of density functionals for future studies on crowded, strained transition states of large molecules.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Yinan Shu, Donald G. Truhlar
Summary: Decoherence refers to the phenomenon where the density matrix of a subsystem evolves into a statistical ensemble of states instead of a coherent combination of pure-state wave functions. In molecular processes involving changes in electronic states and nuclear coordinates, the interaction between the electronic and nuclear subsystems leads to decoherence of the electronic subsystem. This paper provides background information on decoherence and discusses its treatment in the coherent switching with decay of mixing algorithm and the trajectory surface hopping method for semiclassical calculations of electronically nonadiabatic processes.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Computer Science, Interdisciplinary Applications
Yiwei Liu, Cheng Zhang, Zhonghua Liu, Donald G. Truhlar, Ying Wang, Xiao He
Summary: In this study, we optimized a singly hybrid functional called CF22D, which outperforms most existing non-doubly hybrid functionals in terms of accuracy in chemistry. By using a flexible functional form that combines a global hybrid meta-nonseparable gradient approximation with a damped dispersion term, we trained CF22D using a large database and performance-triggered iterative supervised training. The use of a combined database demonstrated CF22D's good performance across various chemical properties and systems.
NATURE COMPUTATIONAL SCIENCE
(2023)
Review
Chemistry, Physical
Indrani Choudhuri, Jingyun Ye, Donald G. Truhlar
Summary: Metal-organic frameworks (MOFs) have exceptional properties for various functions. Experimental characterization and examination of all potentially useful combinations of MOFs are practically impossible. Computational modeling has become an important tool for understanding the functionalization and mechanisms of MOFs.
CHEMICAL PHYSICS REVIEWS
(2023)
Article
Multidisciplinary Sciences
Zhihong Hu, Qimei Di, Bingzhi Liu, Yanbo Li, Yunrui He, Qingbo Zhu, Qiang Xu, Philippe Dagaut, Nils Hansen, S. Mani Sarathy, Lili Xing, Donald G. Truhlar, Zhandong Wang
Summary: Hydroperoxides play crucial roles in atmospheric oxidation, combustion, and catalytic reactions. This study developed a new method for synthesizing organic hydroperoxides and measured their photoionization cross-sections using mass spectrometry. The findings are important for improving chemical models and studying reaction kinetics.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)