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Vibrational ADAPT-VQE: Critical points lead to problematic convergence J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-18 Marco Majland, Patrick Ettenhuber, Nikolaj Thomas Zinner, Ove Christiansen
Quantum chemistry is one of the most promising applications for which quantum computing is expected to have a significant impact. Despite considerable research in the field of electronic structure, calculating the vibrational properties of molecules on quantum computers remains a relatively unexplored field. In this work, we develop a vibrational Adaptive Derivative-Assembled Pseudo-Trotter Variational
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Cation doping and oxygen vacancies in the orthorhombic FeNbO4 material for solid oxide fuel cell applications: A density functional theory study J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-18 Xingyu Wang, David Santos-Carballal, Nora H. de Leeuw
The orthorhombic phase of FeNbO4, a promising anode material for solid oxide fuel cells (SOFCs), exhibits good catalytic activity toward hydrogen oxidation. However, the low electronic conductivity of the material specifically in the pure structure without defects or dopants limits its practical applications as an SOFC anode. In this study, we have employed density functional theory (DFT + U) calculations
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Revisiting fulgide photochromism: Mechanistic decoding and electron transport from computational exploration J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-18 Biman Medhi, Upasana Nath, Manabendra Sarma
The photochromic behavior of the fulgide molecule relies on ring-closure and ring-opening processes involving conical intersections during excited state transformation between isomers. The precise location and topography of these conical intersections significantly shape the decay process and fluorescence phenomena inherent to the molecule. This work combines electronic structure theory calculations
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Thermophysical properties of H2O and D2O ice Ih with contributions from proton disorder, quenching, relaxation, and extended defects: A model case for solids with quenching and relaxation J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-18 W. B. Holzapfel, S. Klotz
Application of the coherent thermodynamic model [W. Holzapfel and S. Klotz, J. Chem. Phys. 155, 024506 (2021)] for H2O ice Ih to the more detailed data for D2O ice Ih provides better insight into the contributions from quenched proton disorder and offers a new basis for understanding the apparent differences between the data for thermal expansion measured with neutron diffraction on polycrystalline
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Pattern dynamics of density and velocity fields in segregation of fluid mixtures J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-18 Prasenjit Das, Awadhesh Kumar Dubey, Sanjay Puri
We present comprehensive numerical results from a study of model H, which describes phase separation kinetics in binary fluid mixtures. We study the pattern dynamics of both density and velocity fields in d = 2, 3. The density length scales show three distinct regimes, in accordance with analytical arguments. The velocity length scale shows a diffusive behavior. We also study the scaling behavior of
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Silver-doped CdSe magic-sized nanocrystals J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-18 Andrew B. Pun, Alexandra J. Lyons, David J. Norris
Magic-sized nanocrystals (MSNCs) grow via jumps between very specific sizes. This discrete growth is a possible avenue toward monodisperse nanomaterials that are completely identical in size and shape. In spite of this potential, MSNCs have seen limited study and application due to their poor optical properties. Specifically, MSNCs are limited in their range of emission wavelengths and commonly exhibit
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Insights into hydrogen and methane storage capacities: Grand canonical Monte Carlo simulations of SIGSUA J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-18 A. Granja-DelRío, I. Cabria
In the pursuit of sustainable energy solutions, the development of materials with efficient hydrogen and methane storage capacities is imperative, particularly for advancing hydrogen-powered vehicles. Metal–organic frameworks (MOFs) have emerged as promising candidates to meet the stringent targets set by the Department of Energy for both hydrogen and methane storage. This study employs Grand Canonical
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h-BN in the making: The surface chemistry of borazine on Rh(111) J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Eva Marie Freiberger, Fabian Düll, Phiona Bachmann, Johann Steinhauer, Federico J. Williams, Hans-Peter Steinrück, Christian Papp
Borazine is a well-established precursor molecule for the growth of hexagonal boron nitride (h-BN) via chemical vapor deposition on metal substrates. To understand the formation of the h-BN/Rh(111) moiré from borazine on a molecular level, we investigated the low-temperature adsorption and thermally induced on-surface reaction of borazine on Rh(111) in situ using synchrotron radiation-based high-resolution
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Self-assembly of chemical shakers J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Liyan Qiao, Raymond Kapral
Chemical shakers are active particles with zero propulsion velocity whose activity derives from chemical reactions on portions of their surfaces. Although they do not move, except through Brownian motion, the nonequilibrium concentration and velocity fields that they generate endow them with properties that differ from their equilibrium counterparts. In particular, collections of such shakers can actively
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Thermodynamics of reversible hydrogen storage: Does alkoxy-substitution of naphthalene yield functional advantages for LOHC systems? J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Sergey P. Verevkin, Artemiy A. Samarov, Sergey V. Vostrikov
The reversible hydrogenation/dehydrogenation of aromatic molecules, known as liquid organic hydrogen carriers (LOHCs), is considered an attractive option for the safe storage and release of elemental hydrogen. The LOHC systems based on the alkoxy-naphthalene/alkoxy-decalin studied in this work can become potentially attractive from the point of view of the thermodynamic conditions of the reversible
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Tin-oxo nanoclusters for extreme ultraviolet photoresists: Effects of ligands, counterions, and doping J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Tingli Du, Xiaowei Yang, Yanyan Zhao, Pingping Han, Jijun Zhao, Si Zhou
The extreme ultraviolet (EUV) nanolithography technology is the keystone for developing the next-generation chips. As conventional chemically amplified resists are approaching the resolution limit, metal-containing photoresists, especially tin-oxo clusters, seize the opportunity to embrace this challenge owing to their small sizes, precise atomic structures, and strong EUV absorption. However, atomistic
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Kinetics of dissociative congruent evaporation based on the transition state theory J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Shiori Inada, Tetsuya Hama, Shogo Tachibana
Non-transition metal oxides, including major minerals of the early Solar System, are known to evaporate decomposing into multiple gas molecules, while maintaining their stoichiometric compositions (dissociative congruent evaporation). Here, we derived the absolute rate of this type of evaporation using the transition state theory. In our modified transition state theory, the activation energy closely
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Microscopic dynamics of gas molecules confined in porous channel-like ice structure J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 L. del Rosso, D. Colognesi, A. Donati, S. Rudić, M. Celli
In the rich ice polymorphism landscape, ice XVII, metastable at ambient pressure and at temperatures below 130 K, is surely one of the most interesting from both fundamental and technological perspectives due to its porosity, i.e., its capability to repeatedly absorb and desorb molecular hydrogen by dosing the gas at pressures even below the ambient one. Here, owing to this exceptional key feature
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Magnetically driven molecular orientational ordering in plastic crystals: The case of d-camphor J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Miao Miao Zhao, Na Du, Yu Ying Zhu, Fei Yen
Many solid crystals exhibit a structural phase transition where a subset of its ions or entire molecules become orientationally ordered. As to why such ordering occurs remains mostly unresolved. We consider the extremely weak magnetic elements arising from the reorientations of the molecules experiencing mutual resonance to play the chief role. Two new features are identified in d-camphor: (1) the
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Microstructural investigation of morphology and kinetics of methane hydrate in the presence of tetrabutylammonium bromide: Insights for preservation and inhibition J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Satoshi Takeya, Sanehiro Muromachi, Michihiro Muraoka, Kiyofumi Suzuki, Norio Tenma, Keiichi Hirano, Kazuyuki Hyodo, Masahide Kawamoto, Akio Yoneyama
Developing highly efficient methane (CH4) hydrate storage methods and understanding the hydrate dissociation kinetics can contribute to advancing CH4 gas storage and transport. The effects of tetrabutylammonium bromide (TBAB) (a thermodynamic promoter) addition on the kinetics of CH4 hydrate were evaluated on the microscopic scale using synchrotron x-ray computed tomography (CT) and powder x-ray diffraction
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Exchange–correlation entropy from the generalized thermal adiabatic connection J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Brittany P. Harding, Zachary Mauri, Vera W. Xie, Aurora Pribram-Jones
Warm dense matter is a highly energetic phase characterized by strong correlations, thermal effects, and quantum mechanical electrons. Thermal density functional theory is commonly used in simulations of this challenging phase, driving the development of temperature-dependent approximations to the exchange–correlation free energy. Approaches using the adiabatic connection formula are well known at
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Characterization of environmental airborne hydrocarbon contaminants by surface-enhanced Raman scattering J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Nathan L. Tolman, Sunny Li, Samuel B. Zlotnikov, Alex D. McQuain, Haitao Liu
This paper explores the unintentional contamination of Surface-Enhanced Raman Scattering (SERS) substrates by ambient hydrocarbon contaminants and their contribution to SERS spectra. Previous studies have identified amorphous carbon as a potential complicating factor in data analysis in SERS experiments, although its origin has been elusive. Our work showed that ambient hydrocarbon contamination and
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MnO(001) thin films on MgO(001) grown by reactive MBE using supersonic molecular beams J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Andrew J. Pedersen, Junchen Liu, Fanxing Li, H. Henry Lamb
MnO(001) thin films were grown on commercial MgO(001) substrates at 520 °C by reactive molecular beam epitaxy (MBE) using Mn vapor and O2-seeded supersonic molecular beams (SMBs) both with and without radio frequency (RF) plasma excitation. For comparison, MnO(001) films were grown by reactive MBE using O2 from a leak valve. X-ray photoelectron spectroscopy confirmed the Mn2+ oxidation state and 10%–15%
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Molecular simulation of flow-enhanced nucleation of polyethylene crystallites in biaxial flows J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-17 Chinmay S Gangal, Gregory C. Rutledge
Flow-enhanced nucleation (FEN) of n-pentacontahectane (C150) under biaxial extensional flows of varying strain rate ratios is studied using nonequilibrium molecular dynamics simulation. The nucleation rates thus calculated are used to test previously published FEN models based on invariants of the conformation tensor of Kuhn segments and the extra stress tensor. Models based on the conformation tensor
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Multiscale modeling of CO2 capture in dicationic ionic liquids: Evaluating the influence of hydroxyl groups using DFT-IR, COSMO-RS, and MD simulation methods J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Mehrangiz Torkzadeh, Majid Moosavi
This work employs a combination of density functional theory-infrared (IR), conductor-like screening model for real solvents (COSMO-RS), and molecular dynamic (MD) methods to investigate the impact of hydroxyl functional groups on CO2 capture within dicationic ionic liquids (DILs). The COSMO-RS reveals that hydroxyl groups in DILs reduce the macroscopic solubility of CO2 but improve the selectivity
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Particle topology-regulated relaxation dynamics in cluster-ordering J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Binghui Xue, Wei Liufu, Jiafu Yin, Junsheng Yang, Panchao Yin
The granular materials of soft particles (SPs) demonstrate unique viscoelasticity distinct from general colloidal and polymer systems. Exploiting dynamic light scattering measurements, together with molecular dynamics simulations, we study the diffusive dynamics of soft particle clusters (SPCs) with spherical and cylindrical brush topologies, respectively, in the melts of SPs. A topologically constrained
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Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Jiarui Ma, Aran Insausti, Mohamad H. Al-Jabiri, Colton D. Carlson, Wolfgang Jäger, Yunjie Xu
The conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol−1 were identified computationally. A rotational spectrum of jet-cooled cis-1,2-cyclohexanediol was recorded with a chirped pulse Fourier transform microwave
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Global machine learning potentials for molecular crystals J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Ivan Žugec, R. Matthias Geilhufe, Ivor Lončarić
Molecular crystals are difficult to model with accurate first-principles methods due to large unit cells. On the other hand, accurate modeling is required as polymorphs often differ by only 1 kJ/mol. Machine learning interatomic potentials promise to provide accuracy of the baseline first-principles methods with a cost lower by orders of magnitude. Using the existing databases of the density functional
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Experimental study of rotational relaxation for D2(1,12) in collisions with N2 J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Lin Mao, Jing Liu, Nurali Habibulla, Yongbao Qiu
The rotational relaxation behavior of D2(1,12) in a D2–N2 mixture was investigated using coherent anti-Stokes Raman scattering (CARS) technique. The rovibrational level v = 1 and J = 12 of D2 was selectively excited through stimulated Raman pumping while monitoring the temporal evolution of population for D2(1, J ≤ 12) molecules using time-resolved CARS spectroscopy. The results demonstrate that the
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Range and sensitivity of 17O nuclear spin-lattice relaxation as a probe of aqueous electrolyte dynamics J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Chengtong Zhang, Alexej Jerschow
The study of electrolytic solutions is of relevance in many research fields, ranging from biophysics, materials, and colloid science to catalysis and electrochemistry. The dependence of solution dynamics on the nature of electrolytes and their concentrations has been the subject of many experimental and computational studies, yet it remains challenging to obtain a full understanding of the factors
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Liquid lasing from solutions of ligand-engineered semiconductor nanocrystals J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Max J. H. Tan, Shreya K. Patel, Jessica Chiu, Zhaoyun Tiffany Zheng, Teri W. Odom
Semiconductor nanocrystals (NCs) can function as efficient gain materials with chemical versatility because of their surface ligands. Because the properties of NCs in solution are sensitive to ligand–environment interactions, local chemical changes can result in changes in the optical response. However, amplification of the optical response is technically challenging because of colloidal instability
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On the lattice ground state of densely packed hard ellipses J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 S. Wagner, G. Kahl, R. Melnyk, A. Baumketner
Among lattice configurations of densely packed hard ellipses, Monte Carlo simulations are used to identify the so-called parallel and diagonal lattices as the two favorable states. The free energies of these two states are computed for several system sizes employing the Einstein crystal method. An accurate calculation of the free energy difference between the two states reveals the parallel lattice
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Accurate diabatization based on combined-hyperbolic-inverse-power-representation: 1,2 2A′ states of BeH2+ J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Yafu Guan, Qun Chen, António J. C. Varandas
A diabatic potential energy matrix (DPEM) for the two lowest states of BeH2+ has been constructed using the combined-hyperbolic-inverse-power-representation (CHIPR) method. By imposing symmetry constraints on the coefficients of polynomials, the complete nuclear permutation inversion symmetry is correctly preserved in the CHIPR functional form. The symmetrized CHIPR functional form is then used in
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Linear response of molecular polaritons J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Joel Yuen-Zhou, Arghadip Koner
In this article, we show that the collective light–matter strong coupling regime where N molecular emitters couple to the photon mode of an optical cavity can be mapped to a quantum impurity model where the photon is the impurity that is coupled to a bath of anharmonic transitions. In the thermodynamic limit where N ≫ 1, we argue that the bath can be replaced with an effective harmonic bath, leading
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Using the Zeno line to assess and refine molecular models J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Thomas Paterson, Marcus N. Bannerman, Leo Lue
The Zeno line is the locus of points on the temperature–density plane where the compressibility factor of the fluid is equal to one. It has been observed to be straight for a broad variety of real fluids, although the underlying reasons for this are still unclear. In this work, a detailed study of the Zeno line and its relation to the vapor–liquid coexistence curve is performed for two simple model
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Chemotactic particles as strong electrolytes: Debye–Hückel approximation and effective mobility law J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Pierre Illien, Ramin Golestanian
We consider a binary mixture of chemically active particles that produce or consume solute molecules and that interact with each other through the long-range concentration fields they generate. We analytically calculate the effective phoretic mobility of these particles when the mixture is submitted to a constant, external concentration gradient, at leading order in the overall concentration. Relying
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Static versus dynamically polarizable environments within the many-body GW formalism J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 David Amblard, Xavier Blase, Ivan Duchemin
Continuum- or discrete-polarizable models for the study of optoelectronic processes in embedded subsystems rely mostly on the restriction of the surrounding electronic dielectric response to its low frequency limit. Such a description hinges on the assumption that the electrons in the surrounding medium react instantaneously to any excitation in the central subsystem, thus treating the environment
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Improving gas adsorption modeling for MOFs by local calibration of Hubbard U parameters J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Yeongsu Cho, Heather J. Kulik
While computational screening with density functional theory (DFT) is frequently employed for the screening of metal–organic frameworks (MOFs) for gas separation and storage, commonly applied generalized gradient approximations (GGAs) exhibit self-interaction errors, which hinder the predictions of adsorption energies. We investigate the Hubbard U parameter to augment DFT calculations for full periodic
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Enhanced thermal conductivity of epoxy resin by incorporating three-dimensional boron nitride thermally conductive network J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Xubin Wang, Changhai Zhang, Tiandong Zhang, Chao Tang, Qingguo Chi
Packaging insulation materials with high thermal conductivity and excellent dielectric properties are favorable to meet the high demand and rapid development of third generation power semiconductors. In this study, we propose to improve the thermal conductivity of epoxy resin (EP) by incorporating a three-dimensional boron nitride thermally conductive network. Detailedly, polyurethane foam (PU) was
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Optical and electronic properties of BCN films deposited by magnetron sputtering J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Caiyun Liu, Le Chen, Hong Yin
Boron carbonitride (BCN) films containing hybridized bonds involving B, C, and N over wide compositional ranges enable an abundant variety of new materials, properties, and applications; however, their electronic performance is still limited by the presence of structural and electronic defects, yielding sluggish mobility and electrical conductivity. This work reports on mechanically stable BCN films
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Plasmon–emitter coupling in cytosine-rich hairpin DNA-templated silver nanoclusters: Thermal reversibility, white light emission, and dynamics inside live cells J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Subhajit Chakraborty, Srikrishna Pramanik, Shashi Shekhar, Saptarshi Mukherjee
Bio-templated luminescent noble metal nanoclusters (NCs) have attracted great attention for their intriguing physicochemical properties. Continuous efforts are being made to prepare NCs with high fluorescence quantum yield (QY), good biocompatibility, and tunable emission properties for their widespread practical applications as new-generation environment-friendly photoluminescent materials in materials
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Formulation of transition dipole gradients for non-adiabatic dynamics with polaritonic states J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 In Seong Lee, Michael Filatov, Seung Kyu Min
A general formulation of the strong coupling between photons confined in a cavity and molecular electronic states is developed for the state-interaction state-average spin-restricted ensemble-referenced Kohn–Sham method. The light–matter interaction is included in the Jaynes–Cummings model, which requires the derivation and implementation of the analytical derivatives of the transition dipole moments
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Unraveling thermodynamic anomalies of water: A molecular simulation approach to probe the two-state theory with atomistic and coarse-grained water models J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Aswin V. Muthachikavil, Gang Sun, Baoliang Peng, Hajime Tanaka, Georgios M. Kontogeorgis, Xiaodong Liang
Thermodynamic and dynamic anomalies of water play a crucial role in supporting life on our planet. The two-state theory attributes these anomalies to a dynamic equilibrium between locally favored tetrahedral structures (LFTSs) and disordered normal liquid structures. This theory provides a straightforward, phenomenological explanation for water’s unique thermodynamic and dynamic characteristics. To
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Prediction Challenge: Simulating Rydberg photoexcited cyclobutanone with surface hopping dynamics based on different electronic structure methods J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Saikat Mukherjee, Rafael S. Mattos, Josene M. Toldo, Hans Lischka, Mario Barbatti
This research examines the nonadiabatic dynamics of cyclobutanone after excitation into the n → 3s Rydberg S2 state. It stems from our contribution to the Special Topic of the Journal of Chemical Physics to test the predictive capability of computational chemistry against unseen experimental data. Decoherence-corrected fewest-switches surface hopping was used to simulate nonadiabatic dynamics with
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The dual nature of metal halide perovskites J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Juan A. Anta, Gerko Oskam, Paul Pistor
Metal halide perovskites have brought about a disruptive shift in the field of third-generation photovoltaics. Their potential as remarkably efficient solar cell absorbers was first demonstrated in the beginning of the 2010s. However, right from their inception, persistent challenges have impeded the smooth adoption of this technology in the industry. These challenges encompass issues such as the lack
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Classification of complex local environments in systems of particle shapes through shape symmetry-encoded data augmentation J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-16 Shih-Kuang (Alex) Lee, Sun-Ting Tsai, Sharon C. Glotzer
Detecting and analyzing the local environment is crucial for investigating the dynamical processes of crystal nucleation and shape colloidal particle self-assembly. Recent developments in machine learning provide a promising avenue for better order parameters in complex systems that are challenging to study using traditional approaches. However, the application of machine learning to self-assembly
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Versatile Cu2ZnSnS4-based synaptic memristor for multi-field-regulated neuromorphic applications J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Xiaofei Dong, Hao Sun, Siyuan Li, Xiang Zhang, Jiangtao Chen, Xuqiang Zhang, Yun Zhao, Yan Li
Integrating both electrical and light-modulated multi-type neuromorphic functions in a single synaptic memristive device holds the most potential for realizing next-generation neuromorphic systems, but is still challenging yet achievable. Herein, a simple bi-terminal optoelectronic synaptic memristor is newly proposed based on kesterite Cu2ZnSnS4, exhibiting stable nonvolatile resistive switching with
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Photodriven electron-transfer dynamics in a series of heteroleptic Cu(I)–anthraquinone dyads J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Brian T. Phelan, Zhu-Lin Xie, Xiaolin Liu, Xiaosong Li, Karen L. Mulfort, Lin X. Chen
Solar fuels catalysis is a promising route to efficiently harvesting, storing, and utilizing abundant solar energy. To achieve this promise, however, molecular systems must be designed with sustainable components that can balance numerous photophysical and chemical processes. To that end, we report on the structural and photophysical characterization of a series of Cu(I)–anthraquinone-based electron
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Two-photon absorption cross sections of pulsed entangled beams J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Frank Schlawin
Entangled two-photon absorption (ETPA) could form the basis of nonlinear quantum spectroscopy at very low photon fluxes, since, at sufficiently low photon fluxes, ETPA scales linearly with the photon flux. When different pairs start to overlap temporally, accidental coincidences are thought to give rise to a “classical” quadratic scaling that dominates the signal at large photon fluxes and, thus, recovers
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The photochemistry of Rydberg-excited cyclobutanone: Photoinduced processes and ground state dynamics J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 J. Eng, C. D. Rankine, T. J. Penfold
Owing to ring strain, cyclic ketones exhibit complex excited state dynamics with multiple competing photochemical channels active on the ultrafast timescale. While the excited state dynamics of cyclobutanone after π* ← n excitation into the lowest-energy excited singlet (S1) state has been extensively studied, the dynamics following 3s ← n excitation into the higher-lying singlet Rydberg (S2) state
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Metasurface-enhanced photochemical activity in visible light absorbing semiconductors J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Yamuna Paudel, Diego J. Chachayma-Farfan, Andrea Alù, Matthew Y. Sfeir
Heterogeneous photocatalysis is an important research problem relevant to a variety of sustainable energy technologies. However, obtaining high photocatalytic efficiency from visible light absorbing semiconductors is challenging due to a combination of weak absorption, transport losses, and low activity. Aspects of this problem have been addressed by multilayer approaches, which provide a general scheme
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Ultrafast restricted intramolecular rotation in molecules with aggregation induced emission J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Xiao Hu, Dongdong Wang, Yanmei Wang, Ye Wang, Song Zhang
In this work, the ultrafast intramolecular rotation behavior of 1,1,2,3,4,5-hexaphenylsilole has been investigated in several solutions with different viscosities using femtosecond transient absorption spectroscopy combined with density functional theory and time-dependent density functional theory calculations. It is demonstrated that the nonradiative process, which competes with radiative decay,
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Confined and spontaneously transformed oxidation structures due to the intrinsic heterogeneous surface morphology of C3N monolayer J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Wenjin Luo, Liang Zhao, Zhijing Huang, Junqing Ni, Yusong Tu
Identifying the oxidation structure of two-dimensional interfaces is crucial to improve surface chemistry and electronic properties. Beyond graphene with only phenyl rings, a novel carbon-nitrogen material, C3N, presents an intrinsic heterogeneous surface morphology where each phenyl ring is encircled by six nitrogen atoms, yet its atomistic oxidation structure remains unclear. Here, combining a series
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Three-metal ion mechanism of cross-linked and uncross-linked DNA polymerase β: A theoretical study J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Wen-Ting Chu, Zucai Suo, Jin Wang
In our recent publication, we have proposed a revised base excision repair pathway in which DNA polymerase β (Polβ) catalyzes Schiff base formation prior to the gap-filling DNA synthesis followed by β-elimination. In addition, the polymerase activity of Polβ employs the “three-metal ion mechanism” instead of the long-standing “two-metal ion mechanism” to catalyze phosphodiester bond formation based
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MesoHOPS: Size-invariant scaling calculations of multi-excitation open quantum systems J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-15 Brian Citty, Jacob K. Lynd, Tarun Gera, Leonel Varvelo, Doran I. G. B. Raccah
The photoexcitation dynamics of molecular materials on the 10–100 nm length scale depend on complex interactions between electronic and vibrational degrees of freedom, rendering exact calculations difficult or intractable. The adaptive Hierarchy of Pure States (adHOPS) is a formally exact method that leverages the locality imposed by interactions between thermal environments and electronic excitations
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Dynamic of binary molecular systems—Advantages and limitations of NMR relaxometry J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-12 Adriane Consuelo Leal Auccaise, Elzbieta Masiewicz, Karol Kolodziejski, Danuta Kruk
1H spin-lattice relaxation studies have been performed for binary systems, including glycerol as the first component and alanine, glycine, and aspartic acid (with different levels of deuteration) as the second one. The relaxation studies have been performed in the frequency range from 10 kHz to 10 MHz vs temperature. A theoretical framework, including all relevant 1H–1H and 1H–2H relaxation pathways
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Near-field coupling of interlayer excitons in MoSe2/WSe2 heterobilayers to surface plasmon polaritons J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-12 Xiong Wang, Zemeng Lin, Kenji Watanabe, Takashi Taniguchi, Wang Yao, Shuang Zhang, Xiaodong Cui
Two-dimensional (2D) transition metal dichalcogenides have emerged as promising quantum functional blocks benefitting from their unique combination of spin, valley, and layer degrees of freedom, particularly for the tremendous flexibility of moiré superlattices formed by van der Waals stacking. These degrees of freedom coupled with the enhanced Coulomb interaction in 2D structures allow excitons to
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Exploring structure–property landscape of non-fullerene acceptors for organic solar cells J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-12 Khantil Patel, Rudranarayan Khatua, Kalyani Patrikar, Anirban Mondal
We present a comprehensive analysis of the structure–property relationship in small molecule non-fullerene acceptors (NFAs) featuring an acceptor–donor–acceptor configuration employing state-of-the-art quantum chemical computational methods. Our focus lies in the strategic functionalization of halogen groups at the terminal positions of NFAs as an effective means to mitigate non-radiative voltage losses
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Assessing the accuracy of TD-DFT excited-state geometries through optimal tuning with GW energy levels J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-11 Iryna Knysh, Denez Raimbault, Ivan Duchemin, Xavier Blase, Denis Jacquemin
We study the accuracy of excited state (ES) geometries using optimally tuned LC-PBE functionals with tuning based on GW quasiparticle energies. We compare the results obtained with the PBE, PBE0, non-tuned, and tuned LC-PBE functionals with available high-level CC reference values as well as experimental data. First, we compare ES geometrical parameters obtained for three different types of systems:
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Collective long-lived zero-quantum coherences in aliphatic chains J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-11 Kirill F. Sheberstov, Anna Sonnefeld, Geoffrey Bodenhausen
In nuclear magnetic resonance, long-lived coherences constitute a class of zero-quantum (ZQ) coherences that have lifetimes that can be longer than the relaxation lifetimes T2 of transverse magnetization. So far, such coherences have been observed in systems with two coupled spins with spin quantum numbers I = 1/2, where a term S0T0+T0S0 in the density operator corresponds to a coherent superposition
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THz spectroscopy on the amino acids L-serine and L-cysteine J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-10 Sebastian Emmert, Peter Lunkenheimer, Alois Loidl
We present a detailed study on the temperature-dependent THz spectra of the polycrystalline amino acids, L-serine and L-cysteine, for wavenumbers from 20 to 120 cm−1 and temperatures from 4 to 300 K. Even though the structure of these two amino acids is very similar, with a sulfur atom in the side chain of cysteine instead of an oxygen atom in serine, the excitation spectra are drastically different
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Multiple-time scale integration method based on an interpolated potential energy surface for ab initio path integral molecular dynamics J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-10 Jingjing Zheng, Michael J. Frisch
A new multiple-time scale integration method is presented that propagates ab initio path integral molecular dynamics (PIMD). This method uses a large time step to generate an approximate geometrical configuration whose energy and gradient are evaluated at the level of an ab initio method, and then, a more precise integration scheme, e.g., the Bulirsch–Stoer method or velocity Verlet integration with
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Coupled cluster-inspired geminal wavefunctions J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-10 Pratiksha B. Gaikwad, Taewon D. Kim, M. Richer, Rugwed A. Lokhande, Gabriela Sánchez-Díaz, Peter A. Limacher, Paul W. Ayers, Ramón Alain Miranda-Quintana
Electron pairs have an illustrious history in chemistry, from powerful concepts to understanding structural stability and reactive changes to the promise of serving as building blocks of quantitative descriptions of the electronic structure of complex molecules and materials. However, traditionally, two-electron wavefunctions (geminals) have not enjoyed the popularity and widespread use of the more
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Multiexcitonic and optically bright states in subunits of pentacene crystals: A hybrid DFT/MRCI and molecular mechanics study J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-10 Timo Schulz, Simon Hédé, Oliver Weingart, Christel M. Marian
A hybrid quantum mechanics/molecular mechanics setup was used to model electronically excited pentacene in the crystal phase. Particularly interesting in the context of singlet fission (SF) is the energetic location of the antiferromagnetically coupled multiexcitonic singlet state, 1(TT), and the ferromagnetically coupled analog in relation to the optically bright singlet state. To provide photophysical
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Evolution of the pentacene exciton band width in pentacene–tetracene blends J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-10 Kateryna Hubenko, Anncharlott Kusber, Marco Naumann, Bernd Büchner, Martin Knupfer
Pentacene is one of the most investigated organic semiconductors. It is well known that the motion of excitons in pentacene and other organic semiconductors is determined by inter-molecular exciton coupling based on charge-transfer processes. In the present study, we demonstrate the impact of the admixture of tetracene, which has a larger band gap and interrupts the pentacene–pentacene interaction