Article
Chemistry, Physical
Bernhard Kretz, David A. Egger
Summary: Accurate non-adiabatic couplings can be calculated using the optimally tuned range-separated hybrid functionals within the framework of linear-response time-dependent density functional theory, providing an efficient alternative to wave-function-based techniques in the modeling of radiationless decay mechanisms in photochemical processes.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Wenna Ai, Wei-Hai Fang, Neil Qiang Su
Summary: This study focuses on the range-separated correlation in long-range corrected hybrid functionals, presenting a theory on its derivation and proving its reliability and effectiveness. The new functional proposed in this work outperforms the traditional LC-BLYP method in various tests and maintains important properties of the XC potential.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Jing Yang, Stefano Falletta, Alfredo Pasquarello
Summary: In this study, the accuracy of range-separated hybrid functionals in predicting band gaps of semiconducting and insulating materials is systematically evaluated and compared with their global counterparts. It is observed that range-separated hybrid functionals that accurately describe long-range dielectric screening significantly outperform standard hybrid functionals such as PBE0 and HSE06. The choice of short-range Fock exchange fraction and screening length can further reduce the prediction error. A universal expression for selecting the inverse screening parameter is proposed, resulting in a mean absolute error as small as 0.15 eV for band gap prediction.
NPJ COMPUTATIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Georgia Prokopiou, Michal Hartstein, Niranjan Govind, Leeor Kronik
Summary: This study focuses on the optimal tuning of free parameters in range-separated double hybrid functionals, aiming to minimize fractional charge and fractional spin errors. The results suggest that introducing range separation in both the exchange and correlation terms is effective in achieving this goal. The optimal set of parameters is system-specific, indicating the importance of the tuning procedure. Additionally, the performance of the optimally tuned functionals in dissociation curves of diatomic molecules is tested, showing an improvement in accuracy.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Susanne Furst, Martin Kaupp
Summary: The recently reported ?LH22t range-separated local hybrid functional can provide results for ionization energies, electron affinities, and fundamental gaps that are comparable to OT-RSH methods, approaching the quality of GW results, without the need for system-specific tuning. This functional also gives excellent outer-valence quasiparticle spectra and is accurate for various excitation types, making it a promising new tool in molecular electronics.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Caroline A. A. McKeon, Samia M. M. Hamed, Fabien Bruneval, Jeffrey B. B. Neaton
Summary: The ab initio GW-BSE approach with optimally tuned range-separated hybrids can suppress starting point dependence for molecules, leading to accuracy similar to higher-order wavefunction-based theories.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Marvin Friede, Sebastian Ehlert, Stefan Grimme, Jan-Michael Mewes
Summary: This study investigates the interdependency between dispersion correction parameters and the range-separation parameter omega in large molecules. The results show that some functionals are strongly affected by omega values, leading to overbinding and poor performance. Strategies to mitigate these issues are discussed, providing insights for future improvements.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Satter Rohman, Rahul Kar
Summary: In this study, computationally inexpensive, nonempirically tuned functionals (ELF* and Sol*) were used to investigate the properties of five organic molecules used in OSLDs. The results showed that ELF* and Sol* functionals accurately reproduced the emission energies in toluene and CBP film environments, while the IP-tuned functional with excited-state geometry performed better in the gas phase. The study also compared different computational methods and reported oscillator strength values.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Tahereh Izadkhast, Mojtaba Alipour
Summary: Predicting non-adiabatic couplings is crucial for studying non-radiative processes. The authors developed and validated optimally tuned range-separated hybrid functionals (OT-RSHs) to accurately calculate non-adiabatic couplings and related properties within time-dependent density functional theory. They found that the OT-RSHs based on specific density functional approximations, incorporating short-range Hartree-Fock exchange, performed the best. These OT-RSHs provide computationally efficient alternatives for studying non-adiabatic systems and screening novel candidates prior to synthesis.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Multidisciplinary Sciences
Rachel Garrick, Leeor Kronik, Tim Gould
Summary: A generalized adiabatic connection for any type of range-separated hybrid functional employed within generalized Kohn-Sham theory is presented, which allows for a rigorous distinction between multiplicative exchange and correlation components. The connection is defined in terms of both generalized and conventional KS orbitals, although using only the KS orbitals introduces a small error in practical calculations. The new adiabatic connection is expected to assist in the development and assessment of RSH functionals.
ADVANCED THEORY AND SIMULATIONS
(2022)
Article
Chemistry, Physical
Moritz Bruetting, Hilke Bahmann, Stephan Kuemmel
Summary: This work explores the self-consistent implementation of a local range-separated hybrid and discusses different forms of the local range-separation function. Experimental results demonstrate that this approach is significantly better than common global range-separated hybrid functionals in terms of atomization energy, reaction barrier height, and total energy of atoms. Furthermore, promising results are obtained for equilibrium bond lengths, harmonic vibrational frequencies, and vertical ionization potentials, highlighting the potential and flexibility of this approach.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Susanne Fuerst, Matthias Haasler, Robin Grotjahn, Martin Kaupp
Summary: We successfully implemented range-separated local hybrid functionals (RSLHs) into the TURBOMOLE program package for the first time, allowing for the computation of ground-state energies, nuclear gradients, and excitation energies. The computational effort of RSLHs is comparable to regular local hybrid functionals (LHs), with a 2-3 times increase in overall timings. The advanced RSLH, omega LH22t, performs well for a wide range of evaluations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Golokesh Santra, Rivka Calinsky, Jan M. L. Martin
Summary: In this study, the performance of 91 density functionals for modeling reaction energies and barrier heights was assessed on a large and diverse dataset. The results showed that range-separated hybrid functionals performed better than global hybrids in predicting barrier heights and reaction energies. The minimally empirical range-separated double hybrid functionals offered slightly better accuracy than the widely used omega B97M(2) for these properties.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Susanne Fuerst, Matthias Haasler, Robin Grotjahn, Martin Kaupp
Summary: We present the implementation of range-separated local hybrid functionals (RSLHs) in TURBOMOLE, allowing for efficient calculation of ground-state and excitation energies. Compared to regular local hybrid functionals (LHs), RSLHs have similar scaling with system or basis set size and increase total timings by a factor of 2-3. A specific RSLH, omega LH22t, is optimized for atomization energies and reaction barriers, showing superior performance for a wide range of ground-state and excited-state quantities. It approaches the accuracy of the best local hybrids to date for various excitation energies and performs remarkably for charge-transfer excitations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Jiawei Zhan, Marco Govoni, Giulia Galli
Summary: Electronic structure calculations based on DFT have successfully predicted ground-state properties of molecules and materials. However, the currently used exchange and correlation functionals are often inaccurate for describing the electronic properties of heterogeneous solids. Here, we present a dielectric-dependent range-separated hybrid functional, SE-RSH, which accurately predicts the electronic structure of various nonmetallic interfaces, solids, and nanoparticles.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Editorial Material
Chemistry, Multidisciplinary
Jean-Luc Bredas, John R. Reynolds
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chen Lu, Eunkyung Cho, Zhiyuan Cui, Yuhang Gao, Wenjuan Cao, Jean-Luc Bredas, Veaceslav Coropceanu, Feng Li
Summary: In contrast to closed-shell luminescent molecules, organic luminescent radicals have both spin doublet electronic states, resulting in spin-allowed radiative transitions. The efficiency and stability of donor-acceptor (D-A center dot) type luminescent radicals, which have a donor group covalently attached to an electron-withdrawing radical core, remain challenging to define. Experimental and theoretical results suggest that the luminescence efficiency and stability of the radicals are determined by the degree of conjugation and the number of imine nitrogen atoms in the substituents, with higher conjugation and lower number of imine nitrogen atoms leading to higher efficiency and stability.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Caroline T. Sargent, Derek P. Metcalf, Zachary L. Glick, Carlos H. Borca, C. David Sherrill
Summary: Using the many-body expansion method, we predicted crystal lattice energies (CLEs) with flexibility in theoretical methods. We computed two-body contributions of 23 molecular crystals using different quantum chemical levels and compared them with coupled-cluster in the complete basis set (CBS) limit. Accurate calculations were achieved for interaction energies of distant dimers using certain methods, reducing the computational expense of coupled-cluster by up to 98%.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Alexander K. Oanta, Kelsey A. Collins, Austin M. Evans, Saied Md Pratik, Lyndon A. Hall, Michael J. Strauss, Seth R. Marder, Deanna M. D'Alessandro, Tijana Rajh, Danna E. Freedman, Hong Li, Jean-Luc Bredas, Lei Sun, William R. Dichtel
Summary: This study introduces a method of embedding electronic spin qubits into two-dimensional polymers and analyzes the spin relaxation times at different spin densities and temperatures. The results show that lower spin densities lead to longer spin relaxation times, while higher spin densities decrease the spin relaxation times. The study demonstrates that dispersing electronic spin qubits within layered 2DPs enables chemical control of their inter-qubit interactions and spin decoherence times.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Julia T. Kohn, Hong Li, Austin M. Evans, Jean-Luc Bredas, Stefan Grimme
Summary: 2D covalent organic frameworks (COFs) possess desirable mechanical and optoelectronic properties, but experimental structure determination remains challenging due to inseparable isomers and limited computational models. In this study, we go beyond the conventional description of COF building blocks and investigate the impact of different stacking and structural motifs on electronic properties. Using the SQM GFN-xTB method, we analyze the structural, energetic, electronic, and spectroscopic results of an imine-linked COF and compare them to experimental findings.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Medicinal
Rameshwar L. Kumawat, C. David Sherrill
Summary: High-order quantum chemistry methods were used to study the intermolecular interaction energies and their components for hydrogen-bonded DNA nucleobase pairs and non-natural Hachimoji nucleobase pairs. The most attractive component of the interaction energies was found to be the electrostatic interactions, followed closely by the sum of induction/polarization and London dispersion. Non-natural Hachimoji base pairs exhibited stronger interactions than the corresponding natural base pairs, while the natural base pairs were more stabilized in their Hoogsteen geometries. Hoogsteen geometries were less favorable for non-natural Hachimoji base pairs compared to Watson-Crick geometries.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Editorial Material
Chemistry, Physical
Michele Ceriotti, Lasse Jensen, David E. Manolopoulos, Todd Martinez, David R. Reichman, Francesco Sciortino, C. David Sherrill, Qiang Shi, Carlos Vega, Lai-Sheng Wang, Emily A. Weiss, Xiaoyang Zhu, Jenny Stein, Tianquan Lian
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Carlos H. Borca, Zachary L. Glick, Derek P. Metcalf, Lori A. Burns, C. David Sherrill
Summary: The use of many-body expansion (MBE) method, combining CCSD(T)/CBS for closest dimers and trimers and MP2 for more distant ones, shows promising results in efficiently calculating lattice energies in organic crystals. The effectiveness of MP2(+ATM) as a replacement for CCSD(T)/CBS is demonstrated. The CCSD(T)/CBS best estimate of the lattice energy at 0 K is -54.01 kJ mol(-1).
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yi Xie, Zachary L. L. Glick, C. David Sherrill
Summary: This study investigates the three-body dispersion contribution to crystal lattice energies in benzene, carbon dioxide, and triazine. By using various computational methods, it is observed that these contributions converge rapidly with increasing intermolecular distances. The closest-contact distance, R-min, shows a strong correlation with the three-body contribution, while R-max is used as a cutoff criterion for considering the number of trimers. The results suggest that the MP2+ATM method can be used to compute trimers with R-min > 4 angstrom to reduce computational cost.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Dominique Lungwitz, Syed Joy, Ahmed E. Mansour, Andreas Opitz, Chamikara Karunasena, Hong Li, Naitik A. Panjwani, Karttikay Moudgil, Kan Tang, Jan Behrends, Stephen Barlow, Seth R. Marder, Jean-Luc Bredas, Kenneth Graham, Norbert Koch, Antoine Kahn
Summary: Evidence is provided by n-doping the polymer P(NDI2OD-T-2) with [RhCp*Cp](2), [N-DMBI](2), and cesium, and studying changes in the electronic structure using ultraviolet photoelectron and low-energy inverse photoemission spectroscopies (UPS, LEIPES). The UPS data shows an additional density of states (DOS) in the former empty polymer gap, while the LEIPES data shows an additional DOS above the conduction band edge. These DOS are assigned to the singly occupied and unoccupied sublevels, allowing determination of a U value of approximately 1eV.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Jianhua Bao, Kaitlyn P. P. Martin, Eunkyung Cho, Kyung-Seok Kang, Richard S. S. Glass, Veaceslav Coropceanu, Jean-Luc Bredas, Wallace O'Neil Parker, Jon T. T. Njardarson, Jeffrey Pyun
Summary: Organosulfur polymers derived from elemental sulfur via the inverse vulcanization process are a new and important class of macromolecules. However, the mechanism of inverse vulcanization and structural characterization of high-sulfur-content copolymers remain challenging. In this study, comprehensive structural characterizations were performed on poly-(S-r-DIB), revealing the incorrect assumptions about its repeating units and the significantly more complex polymerization mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Optics
Li Wan, Rui Zhang, Eunkyung Cho, Hongxiang Li, Veaceslav Coropceanu, Jean-Luc Bredas, Feng Gao
Summary: We propose a widely applicable strategy to fill the spectral gap of circularly polarized light (CPL) detection in the near-infrared (NIR) region by directly inducing chiroptical activity in planar non-fullerene acceptors. This strategy is found to be effective in a wide series of state-of-the-art non-fullerene acceptor families, including ITIC5, o-IDTBR6, and Y6 analogues.
Article
Materials Science, Multidisciplinary
Eunkyung Cho, Saied Md Pratik, Jeffrey Pyun, Veaceslav Coropceanu, Jean-Luc Bredas
Summary: Infrared (IR) thermal imaging is gaining attention for its wide range of applications. Due to the limitations of inorganic materials used for IR imaging, there is a push towards developing organic imaging materials. This study computationally assessed the suitability of pi-conjugated carbon-based materials for long-wave (LW) and mid-wave (MW) IR imaging applications. The results show that fullerenes, graphenes, and double-walled carbon nanotubes are transparent in both LWIR and MWIR regions.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Eunkyung Cho, Veaceslav Coropceanu, Jean-Luc Bredas
Summary: Density functional theory (DFT) calculations reveal that there are no significant differences between the hole and electron transport properties in C60 and C70 and their derivatives. The reorganization energy for hole transport in C70 is slightly lower than for electron transport, and this difference is even larger in functionalized C70 systems. The results suggest that hole mobilities in C70 and its derivatives could be comparable or even larger than the corresponding electron mobilities. Chemical modifications could be exploited to decrease the ionization potential energies of C60 and C70 and facilitate hole injection.
ORGANIC ELECTRONICS
(2023)
Article
Multidisciplinary Sciences
Steven A. Spronk, Zachary L. Glick, Derek P. Metcalf, C. David Sherrill, Daniel L. Cheney
Summary: Fast and accurate calculation of intermolecular interaction energies is crucial for understanding chemical and biological processes. The Splinter dataset, which contains paired molecular fragments representing common substructures in proteins and small-molecule ligands, has been created to facilitate the development and improvement of computational methods for performing these calculations. It is expected to serve as a benchmark dataset for training and testing various methods for calculating intermolecular interaction energies.