Article
Chemistry, Multidisciplinary
Xueguang Ren, Jiaqi Zhou, Enliang Wang, Tao Yang, Zhongfeng Xu, Nicolas Sisourat, Thomas Pfeifer, Alexander Dorn
Summary: Non-covalently bound aromatic systems play a crucial role in biological and technological phenomena, but their molecular dynamics and chemical reactivity in electronic excited states are not fully understood. By observing intermolecular Coulombic decay in benzene dimers, researchers have uncovered the ultrafast relaxation process and dynamics involved in noncovalent pi-pi interactions between aromatic systems.
Article
Chemistry, Multidisciplinary
Fangyuan Zhang, Krzysztof Radacki, Holger Braunschweig, Christoph Lambert, Prince Ravat
Summary: In this study, a novel approach to preparing a discrete dimer of chiral phthalocyanine using the flexible molecular geometry of helicenes was demonstrated. The synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules with high dimerization constants. The study also revealed chiral self-sorting behavior in Zn-7HPc, resulting in preferential formation of a homochiral dimer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Engineering, Environmental
Sheng-Yi Yang, Yuan-Lan Zhang, Fan-Cheng Kong, You-Jun Yu, Hong-Cheng Li, Sheng-Nan Zou, Aziz Khan, Zuo-Quan Jiang, Liang-Sheng Liao
Summary: The novel organic material, Spiro-2P-BT-TPA, exhibits multi-stimulus response properties with potential applications in optoelectronics. It shows high photoluminescence quantum yield in a solid matrix, quasi-aggregation-induced emission, mechanochromic, and solvatochromic properties, making it a promising candidate for OLEDs.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Physical
Rodion Belosludov, Dustin E. Nevonen, Victor N. Nemykin
Summary: The study demonstrated that the hybrid B3LYP functional provides a good compromise for accurate prediction of localized pi-pi* and intramolecular charge-transfer transitions in fully conjugated porphyrin oligomers, allowing confident interpretation of UV-vis-NIR spectra. TDDFT-based sum-over-state calculations correctly predicted the signs and shapes of magnetic circular dichroism signals in the low-energy region of the spectra for porphyrin tape dimers and trimers, along with parent monomers.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Physical
Camilo Zuluaga, Vincent A. Spata, Spiridoula Matsika
Summary: This study compares how 40 different quantum mechanical methods describe the excited states of a guanine-thymine pi-stacked nucleobase dimer system, including both the 5'-TG-3' and 5'-GT-3' conformations. The distance between the nucleobases is found to be a major factor in determining the energy of the CT state and the difference in dipole moments between the CT and ground state. Compared to states localized on one nucleobase, there is a wider range of values (and errors) for the energies of CT states.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Multidisciplinary
Jiahao Chen, Yingtian Xu, Yang Liu, Heng Liu, He Zhang, Liang Jin, Linlin Shi, Yunping Lan, Yonggang Zou, Jie Fan
Summary: This study successfully synthesized a 2D conjugated metal-organic framework and graphene stacked vertical heterostructure. Theoretical simulations and experimental characterizations showed that the charge transfer rate and nonlinear optical properties of this structure were significantly enhanced, demonstrating its potential in the field of ultrafast photonics.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yunzhe Zhou, Zhonghua Deng, Zhenyu Ji, Ziqing Zhang, Cheng Chen, Mingyan Wu
Summary: Triphenylamine and triazine are used to make a pure organic room temperature phosphorescence material (TPATA) with A-(p-D)(3) structure. TPATA exhibits full spectrum photoluminescence by adjusting solvent polarity and can even visually sense halogenated solvents. The photoluminescence band of crystalline TPATA is located at 485 nm, which can compensate for the weak luminescence of commercial white LED devices in this region, and is expected to be applied in LED devices imitating the solar spectrum.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Cheng-Wei Ju, Ethan J. French, Nadav Geva, Alexander W. Kohn, Zhou Lin
Summary: The use of machine learning models has accelerated high-throughput materials and drug discovery based on density functional theory. Compared to nonempirical methods, this new approach has significantly improved in terms of computational efficiency, accuracy, and predictive power.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Xingdong Wang, Jun Hu, Jianhong Lv, Qingqing Yang, Hongkun Tian, Shiyang Shao, Lixiang Wang, Xiabin Jing, Fosong Wang
Summary: Pi-stacked dendrimers with cofacial alignment of donors and acceptors were developed by introducing unique dendritic teracridan donors and triazine acceptors, leading to through-space charge transfer emission with thermally activated delayed fluorescence. By adjusting the charge transfer strength, the emission color of the dendrimers can be tuned, achieving high efficiency two-color white OLEDs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Multidisciplinary
Xue-Qi Wang, Sheng-Yi Yang, Qi-Sheng Tian, Cheng Zhong, Yang-Kun Qu, You-Jun Yu, Zuo-Quan Jiang, Liang-Sheng Liao
Summary: Multi-layer pi-stacked emitters based on spatially confined D/A/D patterns have been developed to achieve high-efficiency TADF. Dual donor moieties and a single acceptor moiety are introduced to form 3D emitters, resulting in high PLQYs, small Delta E-ST, and fast RISC processes. Devices based on these emitters exhibit maximum EQEs higher than their D/A-type analogues.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Taeyeon Kim, Chenjian Lin, Jonathan D. Schultz, Ryan M. Young, Michael R. Wasielewski
Summary: Vibronic coupling is a critical mechanism in photoinduced reactions, but our understanding of its specific impact on excited-state dynamics is lacking. The authors use two-dimensional electronic spectroscopy to investigate vibronic coherences in different types of perylenediimide slip stacks and reveal the complex role of vibronic couplings in tightly packed multimers undergoing a range of photoinduced processes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Biochemistry & Molecular Biology
Evgenii Titov
Summary: The study examines the interactions and electron transition mechanisms of molecules containing azobenzene units in assemblies, finding significant charge transfer contributions under certain conditions. Different methods of partitioning transition density matrix between fragments were evaluated.
Article
Chemistry, Physical
Maria A. Castellanos, Mario Motta, Julia E. Rice
Summary: In this work, the excited state spectra of four aromatic heterocycles were simulated on IBM superconducting quantum computers using the entanglement forging method and the quantum subspace expansion method. The successful application of quantum computing in simulating active-space electronic wavefunctions was demonstrated.
Article
Chemistry, Physical
Montgomery Gray, John M. Herbert
Summary: This study demonstrates that essentially identical results can be obtained using a fast, convenient, and automated tuning procedure based on the size of the exchange hole. In conjunction with extended (X)SAPT methods that improve the dispersion description, this procedure achieves benchmark-quality interaction energies without the hassle of system-specific tuning.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Ayesha Ashraf, John M. Herbert, Shabbir Muhammad, Bilal Ahmad Farooqi, Umar Farooq, Muhammad Salman, Khurshid Ayub
Summary: The interaction mechanism between graphene/nPT composite materials and gaseous analytes CO, NH3, SO2, and NO2 is explored using density functional theory calculations. The change in the highest occupied molecular orbital/lowest unoccupied molecular orbital gap of the composite indicates the change in conductivity upon complexation with the analyte. The computational framework established in this study can be used to evaluate and design gas sensor materials.
Article
Chemistry, Physical
Ying Zhu, John M. Herbert
Summary: In this study, high harmonic spectra for H-2 and H-2(+) were simulated using an atom-centered Gaussian representation of the density and a complex absorbing potential. The results showed that this approach can achieve better resolution compared to grid-based algorithms.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Bushra Alam, Hanjie Jiang, Paul M. Zimmerman, John M. Herbert
Summary: The restricted active space spin-flip (RAS-SF) formalism is a cost-effective method for describing strong correlation in single-reference configuration interaction. In this study, we introduced both equilibrium and nonequilibrium solvation corrections for computing vertical transition energies using RAS-SF wave functions. Benchmark calculations were performed for various photo-induced charge transfer models, and the results demonstrate the importance of the RAS-SF + PCM methodology in studying charge-separated states in solution and photovoltaic materials.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Montgomery Gray, John M. Herbert
Summary: This study systematically investigates the convergence of XSAPT interaction energies and energy components with respect to the choice of Gaussian basis sets. Errors can be reduced using correlation-consistent basis sets and new versions with limited augmentation. The use of Pople-style basis sets may afford good results if a large number of polarization functions are included.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Kevin Carter-Fenk, John M. Herbert
Summary: In this study, we propose improvements to the dispersion damping potentials in the effective fragment potential (EFP) and evaluate their performance using a new database of ionic liquid constituents. We recommend a new parameter-free dispersion damping function as a replacement for the current one used in EFP.
Article
Chemistry, Physical
Bhaskar Rana, Gregory J. O. Beran, John M. Herbert
Summary: This study considers molecules with pi-electron conjugation and finds that delocalisation error in density functional theory affects their conformational energies. By using density-corrected methods, the errors can be significantly reduced, enabling accurate calculations of molecular crystals.
Article
Chemistry, Physical
Montgomery Gray, John M. Herbert
Summary: This study investigates the interaction energies and components in porous frameworks and finds that the van der Waals interaction is the main driving force for parallel-displaced pi-stacking, while electrostatics plays a minor role. The presence of a guest molecule limits the available slip-stacking configurations in COF-1.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Kevin Carter-Fenk, Britta A. Johnson, John M. Herbert, Gregory K. Schenter, Christopher J. Mundy
Summary: A new simulation method is used to directly study the generation of hydrated electrons from the charge-transfer-to-solvent state. The simulations reveal a two-step process involving ionization and solute reorganization leading to the equilibrated ground state of the solvated electron. This methodology has implications for photochemical electron transfer processes in solution, with potential application in photocatalysis and energy transfer.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Subrata Jana, John M. M. Herbert
Summary: The methods for computing core-level ionization energies are evaluated and compared. The full core hole approach and Slater's transition concept are considered, with the latter showing mean errors of 0.3-0.4 eV compared to experiment. A shifted Slater transition method requiring only initial-state Kohn-Sham eigenvalues is found to be a simple and practical way to compute core-level binding energies. It is particularly useful for simulating transient x-ray experiments.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Subrata Jana, John M. M. Herbert
Summary: This article examines methods for calculating X-ray absorption spectra using a constrained core hole, which may contain a fractional electron. These methods are based on Slater's transition concept and generalize it by using Kohn-Sham orbital energies to determine core-to-valence excitation energies. The tested methods achieve robust convergence by avoiding promoting electrons beyond the lowest unoccupied molecular orbital. The best-case accuracy of these methods is found to be 0.3-0.4 eV with respect to experiment for K-edge transition energies. Higher-lying near-edge transitions have larger absolute errors, but these can be reduced below 1 eV by introducing an empirical shift based on a charge-neutral transition-potential method combined with specific functionals like SCAN, SCAN0, or B3LYP. This procedure allows for obtaining an entire excitation spectrum from a single fractional-electron calculation, without the need for state-by-state calculations based on ground-state density functional theory. The shifted transition-potential approach proposed in this study is particularly useful for simulating transient spectroscopies and in complex systems where excited-state Kohn-Sham calculations are challenging.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Paige E. Bowling, Dustin R. Broderick, John M. Herbert
Summary: Electronic structure calculations on enzymes with hundreds of atoms can be costly, but fragment-based approximations provide a cost-effective solution. The many-body expansion method allows calculations on enzyme models with 500-600 atoms and compares well with benchmarks. Different boundary conditions can affect the convergence of the calculations, highlighting the need for appropriate assessments of errors in fragment-based approximations. Protocols involving three-body or two-body calculations combined with a full-system correction offer accurate results at a lower computational cost, making high-level quantum chemistry applicable to large systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Correction
Chemistry, Physical
Kevin Carter-Fenk, Britta A. Johnson, John M. Herbert, Gregory K. Schenter, Christopher J. Mundy
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Dustin R. Broderick, John M. Herbert
Summary: The many-body expansion is a method used to calculate electronic structure in large systems. This study presents an algorithm to overcome the combinatorial bottleneck in many-body expansion and implements it in a software application called Fragment. The results show that this method allows for unprecedentedly large-scale calculations with high accuracy.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Paige E. Bowling, Dustin R. Broderick, John M. Herbert
Summary: Electronic structure calculations on enzymes are improved by fragment-based approximations and many-body expansion. When using amino acid fragments with ionic side chains, low-dielectric boundary conditions are necessary to restore rapid convergence. Traditional gas-phase calculations do not provide accurate benchmarks for assessing errors in fragment-based approximations. Three-body and two-body protocols with a full-system correction achieve high-level quantum chemistry calculations on large systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Montgomery Gray, John M. Herbert
Summary: In this study, the slip-stacking in porous frameworks, such as COF-1, is investigated by computing interaction energies and their components. It is found that the van der Waals interaction potential drives the system into a slip-stacked geometry, while electrostatics only plays a minor role. Even in the absence of solvent molecules, a modest lateral offset is preferred in COF-1.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)