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Fourier–Matsubara series expansion for imaginary–time correlation functions J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-08 Panagiotis Tolias, Fotios Kalkavouras, Tobias Dornheim
A Fourier–Matsubara series expansion is derived for imaginary–time correlation functions that constitutes the imaginary–time generalization of the infinite Matsubara series for equal-time correlation functions. The expansion is consistent with all known exact properties of imaginary–time correlation functions and opens up new avenues for the utilization of quantum Monte Carlo simulation data. Moreover
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Spectroscopic analysis of the sum-frequency response of the carbon–hydrogen stretching modes in collagen type I J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-08 Yryx Y. Luna Palacios, Salile Khandani, Evan P. Garcia, Anabel Chen, Siyang Wang, Khokan Roy, David Knez, Do A. Kim, Israel Rocha-Mendoza, Eric O. Potma
We studied the origin of the vibrational signatures in the sum-frequency generation (SFG) spectrum of fibrillar collagen type I in the carbon–hydrogen stretching regime. For this purpose, we developed an all-reflective, laser-scanning SFG microscope with minimum chromatic aberrations and excellent retention of the polarization state of the incident beams. We performed detailed SFG measurements of aligned
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First-principles studies on the process of electron transfer between hydrophobic liquids and water J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-08 Zhe Yang, Yang Nan, Morten Willatzen, Zhong Lin Wang
Using the density functional theory, we conducted a study on the electrification upon contact between hydrophobic liquid molecules and water molecules, revealing localized characteristics of contact-electrification. These “localized features” refer to the specific microscale characteristics where electron transfer predominantly occurs at the contact regions, influenced by factors such as atomic distances
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Escape from textured adsorbing surfaces J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-08 Yuval Scher, Shlomi Reuveni, Denis S. Grebenkov
The escape dynamics of sticky particles from textured surfaces is poorly understood despite importance to various scientific and technological domains. In this work, we address this challenge by investigating the escape time of adsorbates from prevalent surface topographies, including holes/pits, pillars, and grooves. Analytical expressions for the probability density function and the mean of the escape
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Current density functional framework for spin–orbit coupling: Extension to periodic systems J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-08 Yannick J. Franzke, Christof Holzer
Spin–orbit coupling induces a current density in the ground state, which consequently requires a generalization for meta-generalized gradient approximations. That is, the exchange–correlation energy has to be constructed as an explicit functional of the current density, and a generalized kinetic energy density has to be formed to satisfy theoretical constraints. Herein, we generalize our previously
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Pillared graphene oxide frameworks for the adsorption and separation of polar protic and aprotic liquid solvents: The cases of pure water, methanol, dimethyl sulfoxide, and dimethyl sulfoxide–water mixtures J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-08 Ioannis Skarmoutsos, Emmanuel N. Koukaras, Emmanuel Klontzas
Potential applications of previously synthesized pillared graphene oxide frameworks with phenyldiboronic acid linkers in the field of the adsorption and separation of polar protic and aprotic liquid solvents have been systematically explored using grand canonical Monte Carlo simulations. Particular attention was initially paid to the adsorption of pure liquid water, methanol, and dimethyl sulfoxide
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Generic low-density corrections to the equation of state of chain molecules with repulsive intermolecular forces J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Thijs van Westen, Philipp Rehner, Thijs J. H. Vlugt, Joachim Gross
Molecular-based equations of state for describing the thermodynamics of chain molecules are often based on mean-field like arguments that reduce the problem of describing the interactions between chains to a simpler one involving only nonbonded monomers. While for dense liquids such arguments are known to work well, at low density they are typically less appropriate due to an incomplete description
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Semiclassical approaches to perturbative time-convolution and time-convolutionless quantum master equations for electronic transitions in multistate systems J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Xiang Sun, Zengkui Liu
Understanding the dynamics of photoinduced processes in complex systems is crucial for the development of advanced energy-conversion materials. In this study, we investigate the nonadiabatic dynamics using time-convolution (TC) and time-convolutionless (TCL) quantum master equations (QMEs) based on treating electronic couplings as perturbation within the framework of multistate harmonic (MSH) models
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Measuring friction from simulations of folded graphene sheets J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Charlie M. Rawlins, Gareth A. Tribello
We ran molecular dynamics simulations of folded graphene sheets and present a procedure to measure the sliding friction in these systems based on the rate of decay of a damped harmonic oscillator. This procedure allowed us to study the effect that the size, geometry, and the temperature of the graphene sheet had on the ability to propagate the initial fold and the rate at which it settles to a final
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The rates of non-adiabatic processes in large molecular systems: Toward an effective full-dimensional quantum mechanical approach J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Alessandro Landi, Andrea Landi, Anna Leo, Andrea Peluso
Two computational approaches for computing the rates of internal conversions in molecular systems where a large set of nuclear degrees of freedom plays a role are discussed and compared. One approach is based on the numerical solution of the time-dependent Schrödinger equation and allows us to include almost the whole set of vibrational coordinates, thanks to the employment of effective procedures
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Photoluminescence study of anatase TiO2 photocatalysts at the pico- and nanosecond timescales J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Ryuzi Katoh, Kazuhiko Seki
We studied the photoluminescence decay kinetics of three nanosized anatase TiO2 photocatalysts (particle diameter: 7, 25, or 200 nm) at the pico- and nanosecond timescales for elucidating the origin of the luminescence. Luminescence spectra from these photocatalysts obtained under steady-state excitation conditions comprised green luminescence that decayed on the picosecond timescale and red luminescence
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Predicting the artificial dynamical acceleration of binary hydrocarbon mixtures upon coarse-graining with roughness volumes and simple averaging rules J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Melissa K. Meinel, Florian Müller-Plathe
Coarse-grained (CG) molecular models greatly reduce the computational cost of simulations allowing for longer and larger simulations, but come with an artificially increased acceleration of the dynamics when compared to the parent atomistic (AA) simulation. This impedes their use for the quantitative study of dynamical properties. During coarse-graining, grouping several atoms into one CG bead not
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A MASH simulation of the photoexcited dynamics of cyclobutanone J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Joseph E. Lawrence, Imaad M. Ansari, Jonathan R. Mannouch, Meghna A. Manae, Kasra Asnaashari, Aaron Kelly, Jeremy O. Richardson
In response to a community prediction challenge, we simulate the nonadiabatic dynamics of cyclobutanone using the mapping approach to surface hopping (MASH). We consider the first 500 fs of relaxation following photoexcitation to the S2 state and predict the corresponding time-resolved electron-diffraction signal that will be measured by the planned experiment. 397 ab initio trajectories were obtained
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Size-dependent photoluminescence blinking mechanisms and volume scaling of biexciton Auger recombination in single CsPbI3 perovskite quantum dots J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Changgang Yang, Guofeng Zhang, Yunan Gao, Bin Li, Xue Han, Jialu Li, Mi Zhang, Zhihao Chen, Yixin Wei, Ruiyun Chen, Chengbing Qin, Jianyong Hu, Zhichun Yang, Ganying Zeng, Liantuan Xiao, Suotang Jia
Determining the correlation between the size of a single quantum dot (QD) and its photoluminescence (PL) properties is a challenging task. In the study, we determine the size of each QD by measuring its absorption cross section, which allows for accurate investigation of size-dependent PL blinking mechanisms and volume scaling of the biexciton Auger recombination at the single-particle level. A significant
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State-to-state dynamics and machine learning predictions of inelastic and reactive O(3P) + CO(1∑+) collisions relevant to hypersonic flows J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Xia Huang, Xinlu Cheng
The state-to-state (STS) inelastic energy transfer and O-atom exchange reaction between O and CO(v), as two fundamental processes in non-equilibrium air flow around spacecraft entering Mars’ atmosphere, yield the same products and both make significant contributions to the O + CO(v) → O + CO(v′) collisions. The inelastic energy transfer competes with the O-atom exchange reaction. The detailed reaction
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The updates in Libcint 6: More integrals, API refinements, and SIMD optimization techniques J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Qiming Sun
Libcint is a library designed for the evaluation of analytical integrals for Gaussian type orbitals. It prioritizes simplicity, ease of use, and efficiency for the development of quantum chemistry programs. In the release of version 6.0, Libcint supports the computation of integrals for various operators, such as overlap, Coulomb, Gaunt, Breit, attenuated Coulomb, Slater-type geminals, and Yukawa potential
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Elucidating the structural and conformational preferences of bioactive chromone and its monohydrate through advanced rotational spectroscopy J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Junhua Chen, Min Zhang, Junlin Lan, Chengxu Wang, Zhikai Chen, Xuefang Xu, Xiuli Gao, Qian Gou
Chromones are a class of naturally occurring compounds, renowned for their diverse biological activities with significant relevance in medicine and biochemistry. This study marks the first analysis of rotational spectra of both the chromone monomer and its monohydrate through Fourier transform microwave spectroscopy. The observation of nine mono-substituted 13C isotopologues facilitated a semi-experimental
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State-selective dissociative double ionization of CH3I and CH2I2 via I 4d core-hole states studied by multi-electron–ion coincidence spectroscopy J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Mizuho Fushitani, Yasumasa Hikosaka, Motomichi Tashiro, Akiyoshi Hishikawa
The dissociative double ionization of CH3I and CH2I2 irradiated with extreme ultraviolet light at hv = 100 eV is investigated by multi-electron–ion coincidence spectroscopy using a magnetic bottle type electron spectrometer. The spin–orbit state-resolved Auger electron spectra for the I 4d core-hole states, (I 4d3/2)−1 and (I 4d5/2)−1, provide clear identifications of electronic states of CH3I2+ and
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Non-adiabatic direct quantum dynamics using force fields: Toward solvation J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 L. L. E. Cigrang, J. A. Green, S. Gómez, J. Cerezo, R. Improta, G. Prampolini, F. Santoro, G. A. Worth
Quantum dynamics simulations are becoming a powerful tool for understanding photo-excited molecules. Their poor scaling, however, means that it is hard to study molecules with more than a few atoms accurately, and a major challenge at the moment is the inclusion of the molecular environment. Here, we present a proof of principle for a way to break the two bottlenecks preventing large but accurate simulations
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Dynamic density functional theory with inertia and background flow J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 R. D. Mills-Williams, B. D. Goddard, A. J. Archer
We present dynamic density functional theory (DDFT) incorporating general inhomogeneous, incompressible, time-dependent background flows and inertia, describing externally driven passive colloidal systems out of equilibrium. We start by considering the underlying nonequilibrium Langevin dynamics, including the effect of the local velocity of the surrounding liquid bath, to obtain the nonlinear, nonlocal
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Dual-level strategy for quantitative kinetics for the reaction between ethylene and hydroxyl radical J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Junxian Li, Bo Long
The atmospheric reactions are mainly initiated by hydroxyl radical (OH). Here, we choose the C2H4 + OH reaction as a model reaction for other reactions of OH with alkenes. We use the GMM(P).L//CCSD(T)-F12a/cc-pVTZ-F12 theoretical method as the benchmark results close to the approximation of CCSDTQ(P)/CBS accuracy to investigate the C2H4 + OH reaction. The rate constants for the C2H4 + OH reaction at
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Heterogeneous hydrochlorination of lipids mediated by fatty acids in an indoor environment J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Yaqi Liu, Zhuo Liu, Yijing Chen, Jing He, Yuqing Niu, Yuwei He, Yanjie Wang, Yun Ju, Jie Jiang, Hong Zhang, Lina Qiao
Fatty acids from cooking fumes and hypochlorous acid (HOCl) released from indoor cleaning adversely affect respiratory health, but the molecular-level mechanism remains unclear. Here, the effect of cooking oil fumes [palmitic acid (PA), oleic acid (OA), and linoleic acid (LA)] on lung model phospholipid (POPG) hydrochlorination mediated by HOCl at the air–water interface of the hanged droplets was
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Beyond isotropic repulsion: Classical anisotropic repulsion by inclusion of p orbitals J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Moses K. J. Chung, Jay W. Ponder
Accurate modeling of intermolecular repulsion is an integral component in force field development. Although repulsion can be explicitly calculated by applying the Pauli exclusion principle, this approach is computationally viable only for systems of limited sizes. Instead, it has previously been shown that repulsion can be reformulated in a “classical” picture: the Pauli exclusion principle prohibits
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Grid: A Python library for molecular integration, interpolation, differentiation, and more J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Alireza Tehrani, Xiaotian Derrick Yang, Marco Martínez-González, Leila Pujal, Raymundo Hernández-Esparza, Matthew Chan, Esteban Vöhringer-Martinez, Toon Verstraelen, Paul W. Ayers, Farnaz Heidar-Zadeh
Grid is a free and open-source Python library for constructing numerical grids to integrate, interpolate, and differentiate functions (e.g., molecular properties), with a strong emphasis on facilitating these operations in computational chemistry and conceptual density functional theory. Although designed, maintained, and released as a stand-alone Python library, Grid was originally developed for molecular
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APOST-3D: Chemical concepts from wavefunction analysis J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 P. Salvador, E. Ramos-Cordoba, M. Montilla, L. Pujal, M. Gimferrer
Open-source APOST-3D software features a large number of wavefunction analysis tools developed over the past 20 years, aiming at connecting classical chemical concepts with the electronic structure of molecules. APOST-3D relies on the identification of the atom in the molecule (AIM), and several analysis tools are implemented in the most general way so that they can be used in combination with any
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Electronic structure and optical spectral analysis of the MnO42− anion with consideration of site and Jahn–Teller distortion J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Ronald L. Birke
The ground state of 3d1 MnO42− was studied by density functional theory (DFT) and complete active space self-consistent field (CASSCF) methods in terms of a variety of molecular point group structures to ascertain the site and Jahn–Teller (JT) distortion effect. Modeling results from UB3LYP/6-31+G(d) calculations with natural bond orbital analysis show the four Mn–O bonds are coordinate covalent. The
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The influence of stereodynamical control on the nonadiabatic effects in the D + HD (v = 1, j = 2) → D2 + H reaction J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Xiaoxi Xu, Zijiang Yang, Bayaer Buren, Maodu Chen
Stereodynamics is a field that studies the influence of the alignment or orientation of colliding partners on the results of collisions. At present, the intersection of nonadiabatic effects and stereodynamics remains to be explored. In this study, we theoretically demonstrate significant stereodynamical effects in the D + HD (v = 1, j = 2) → D2 + H reaction within the collision energy range of 0.01–2
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Revealing the reconstruction mechanism of AgPd nanoalloys under fluorination based on a multiscale deep learning potential J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Longfei Guo, Shuang Shan, Xiaoqing Liu, Wanxuan Zhang, Peng Xu, Fanzhe Ma, Zhen Li, Chongyang Wang, Junpeng Wang, Fuyi Chen
The design of heterogeneous catalysts generally involves optimizing the reactivity descriptor of adsorption energy, which is inevitably governed by the structure of surface-active sites. A prerequisite for understanding the structure–properties relationship is the precise identification of real surface-active site structures, rather than relying on conceived structures derived from bulk alloy properties
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A model of heterogeneous undercooled liquid and glass accounting for temperature-dependent nonexponentiality and enthalpy fluctuation J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Wataru Takeda, Pierre Lucas
Dynamic heterogeneity is a fundamental characteristic of glasses and undercooled liquids. The heterogeneous nature causes some of the key features of systems’ dynamics such as the temperature dependence of nonexponentiality and spatial enthalpy fluctuations. Commonly used phenomenological models such as Tool–Narayanaswamy–Moynihan (TNM) and Kovacs–Aklonis–Hutchinson–Ramos fail to fully capture this
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Stochastic distinguishability of Markovian trajectories J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Asawari Pagare, Zhongmin Zhang, Jiming Zheng, Zhiyue Lu
The ability to distinguish between stochastic systems based on their trajectories is crucial in thermodynamics, chemistry, and biophysics. The Kullback–Leibler (KL) divergence, DKLAB(0,τ), quantifies the distinguishability between the two ensembles of length-τ trajectories from Markov processes A and B. However, evaluating DKLAB(0,τ) from histograms of trajectories faces sufficient sampling difficulties
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Oblique impingement of binary droplets at the nanoscale on superhydrophobic surfaces: A molecular dynamics study J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Aiping Zhang, Kai Cui, Yuanyuan Tian, Benxi Zhang, Tieying Wang, Xin He
The impacting phenomenon of nanodroplets has received much attention due to their importance in various industrial applications. The oblique impingement of single droplets is well understood; however, the effect of oblique angle on impacting the dynamics of multiple droplets at the nanoscale is very limited. To address this gap, we perform molecular dynamics (MD) simulations to study the impacting
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A bivariational, stable, and convergent hierarchy for time-dependent coupled cluster with adaptive basis sets J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Mads Greisen Højlund, Ove Christiansen
We propose a new formulation of time-dependent coupled cluster with adaptive basis functions and division of the one-particle space into active and secondary subspaces. The formalism is fully bivariational in the sense of a real-valued time-dependent bivariational principle and converges to the complete-active-space solution, a property that is obtained by the use of biorthogonal basis functions. A
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Statistical theory of fluids confined in quenched disordered porous media J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Mamta Yadav, Ankit Singh, Yashwant Singh
We develop a theory to calculate structural correlations and thermodynamic properties of a fluid confined in a random porous solid medium (matrix). We used density functional formalism to derive an annealed averaged expression for the density profile and excess free energy of fluid arising due to random fields of a particular realization of the matrix. After performing the second average over the quenched-disordered
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Resonant Auger decay of iodobenzene below the I 4d edge J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Stephen T. Pratt, Ugo Jacovella, Bérenger Gans, John D. Bozek, David M. P. Holland
New data are presented on the resonant Auger decay of iodobenzene (C6H5I) in the region of the I 4d−1 ionization threshold. The excited molecules decay by participator and spectator processes to populate single-hole valence states and two-hole, one-particle excited states of the cation, providing new information on the structure of C6H5I+. Excitation of dissociative C6H5I (I 4d5/2,3/2−1)σ* resonances
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Multiparticle collision dynamics simulations of hydrodynamic interactions in colloidal suspensions: How well does the discrete particle approach do at short range? J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Ying-Shuo Peng, Talid Sinno
The multiparticle collision dynamics (MPCD) simulation method is an attractive technique for studying the effects of hydrodynamic interactions in colloidal suspensions because of its flexibility, computational efficiency, and ease of implementation. Here, we analyze an extension of the basic MPCD method in which colloidal particles are discretized with a surface mesh of sensor nodes/particles that
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Perspective: Atomistic simulations of water and aqueous systems with machine learning potentials J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Amir Omranpour, Pablo Montero De Hijes, Jörg Behler, Christoph Dellago
As the most important solvent, water has been at the center of interest since the advent of computer simulations. While early molecular dynamics and Monte Carlo simulations had to make use of simple model potentials to describe the atomic interactions, accurate ab initio molecular dynamics simulations relying on the first-principles calculation of the energies and forces have opened the way to predictive
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Cascading symmetry constraint during machine learning-enabled structural search for sulfur-induced Cu(111)-(43×43) surface reconstruction J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Florian Brix, Mads-Peter Verner Christiansen, Bjørk Hammer
In this work, we investigate how exploiting symmetry when creating and modifying structural models may speed up global atomistic structure optimization. We propose a search strategy in which models start from high symmetry configurations and then gradually evolve into lower symmetry models. The algorithm is named cascading symmetry search and is shown to be highly efficient for a number of known surface
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Dissipative particle dynamics for coarse-grained models J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Tine Curk
We develop a computational method based on Dissipative Particle Dynamics (DPD) that introduces solvent hydrodynamic interactions to coarse-grained models of solutes, such as ions, molecules, or polymers. DPD-solvent (DPDS) is a fully off-lattice method that allows straightforward incorporation of hydrodynamics at desired solvent viscosity, compressibility, and solute diffusivity with any particle-based
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Unveiling interatomic distances influencing the reaction coordinates in alanine dipeptide isomerization: An explainable deep learning approach J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Kazushi Okada, Takuma Kikutsuji, Kei-ichi Okazaki, Toshifumi Mori, Kang Kim, Nobuyuki Matubayasi
The present work shows that the free energy landscape associated with alanine dipeptide isomerization can be effectively represented by specific interatomic distances without explicit reference to dihedral angles. Conventionally, two stable states of alanine dipeptide in vacuum, i.e., C7eq (β-sheet structure) and C7ax (left handed α-helix structure), have been primarily characterized using the main
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A new dynamic Monte Carlo method satisfying n-particle diffusion equation with position-dependent diffusion coefficient, free energy, and intermolecular interactions J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-07 Susumu Okazaki
A dynamic Monte Carlo (MC) method recently proposed by us [Nagai et al., J. Chem. Phys. 156, 154506 (2022)] to describe single-particle diffusion of a molecule in a heterogeneous space with position-dependent diffusion coefficient and free energy is generalized here to n-particle dynamics, where n molecules diffuse in heterogeneous media interacting via their intermolecular potential. Starting from
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Interference is in the eye of the beholder: Application to the coherent control of collisional processes J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Adrien Devolder, Timur V. Tscherbul, Paul Brumer
Interference is widely regarded as a foundational attribute of quantum mechanics. However, for a given experimental arrangement, interference can either contribute or not contribute to the outcome depending upon the basis in which it is measured. This observation is both foundational and particularly relevant to coherent control of molecular processes, an approach based upon quantum interference. Here
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ABLRI: A program for calculating the long-range interaction energy between two monomers in their non-degenerate states J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Yipeng Yu, Dongzheng Yang, Xixi Hu, Daiqian Xie
An accurate description of the long-range (LR) interaction is essential for understanding the collision between cold or ultracold molecules. However, to our best knowledge, there lacks a general approach to construct the intermolecular potential energy surface (IPES) between two arbitrary molecules and/or atoms in the LR region. In this work, we derived analytical expressions of the LR interaction
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Insights into thiocyanate-enhanced photoluminescence in CsPbBr3 nanocrystals by ultrafast two-dimensional infrared spectroscopy J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Arghyadeep Basu, Nathan Rafisiman, Saar Shaek, Rachel Lifer, Vivek Yadav, Yaron Kauffmann, Yehonadav Bekenstein, Lev Chuntonov
Functionalization of perovskite nanocrystal surfaces with thiocyanate anions presents a transformative approach to enhancing stability and photoluminescence quantum yield (PLQY) through surface defect passivation. This study investigates the role of thiocyanate ligands in modifying the optoelectronic properties of CsPbBr3 nanocrystals. We employed ultrafast two-dimensional infrared spectroscopy to
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Variational umbrella seeding for calculating nucleation barriers J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Willem Gispen, Jorge R. Espinosa, Eduardo Sanz, Carlos Vega, Marjolein Dijkstra
In this work, we introduce variational umbrella seeding, a novel technique for computing nucleation barriers. This new method, a refinement of the original seeding approach, is far less sensitive to the choice of order parameter for measuring the size of a nucleus. Consequently, it surpasses seeding in accuracy and umbrella sampling in computational speed. We test the method extensively and demonstrate
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Exploring electron donor and acceptor effects: DFT analysis of ESIPT/GSIPT in 2-(oxazolinyl)-phenols for photophysical and luminophore enhancement J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Murugesan Panneerselvam, Reshma Rensil Francis, Singaravel Nathiya, Rajadurai Vijay Solomon, Madhavan Jaccob, Luciano T. Costa
Understanding excited-state intramolecular proton transfer (ESIPT) is essential for designing organic molecules to enhance photophysical and luminophore properties in the development of optoelectronic devices. In this context, an attempt has been made to understand the impact of substituents on the ESIPT process of 2-(oxazolinyl)-phenol. Electron donating (EDG: –NH2, –OCH3, and –CH3) and electron withdrawing
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Thermodynamics of the gas-phase dimerization of formic acid: Fully anharmonic finite temperature calculations at the CCSD(T) and many DFT levels J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Dávid Vrška, Michal Pitoňák, Tomáš Bučko
A proof-of-concept study is undertaken to demonstrate the utility of the machine learning combined with the thermodynamic perturbation theory (MLPT) to test the accuracy of electronic structure methods in finite-temperature thermodynamic calculations. As a test example, formic acid dimer is chosen, which is one of the systems included in the popular benchmark set S22 [Jurečka et al., Phys. Chem. Chem
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Exploration of Stokes hydrodynamic law at molecular length scales J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Subhajit Acharya, Biman Bagchi
The celebrated generalized Stokes law predicts that the velocity of a particle pulled through a liquid by an external force, Fex, is directly proportional to the force and inversely proportional to the friction ζ acted by the medium on the particle. We investigate the range of validity of the generalized Stokes law at molecular length scales by employing computer simulations to calculate friction by
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Simple and efficient methods for local structural analysis in polydisperse hard disk systems J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Daigo Mugita, Kazuyoshi Souno, Hiroaki Koyama, Taisei Nakamura, Masaharu Isobe
In nonequilibrium statistical physics, quantifying the nearest (and higher-order) neighbors and free volumes of particles in many-body systems is crucial to elucidating the origin of macroscopic collective phenomena, such as glass/granular jamming transitions and various aspects of the behavior of active matter. However, conventional techniques (based on a fixed-distance cutoff or the Voronoi construction)
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Fundamental equation of state for mixtures of nitrogen, oxygen, and argon based on molecular simulation data J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Monika Thol, Sven Michael Pohl, Denis Saric, Roland Span, Jadran Vrabec
A fundamental equation of state in terms of the Helmholtz energy is presented for mixtures of nitrogen, oxygen, and argon at any composition. It is expressed in terms of the residual Helmholtz energy and can be used to calculate all thermodynamic equilibrium properties including vapor–liquid equilibria. The parameters of the equations for the pure-fluid and mixture contributions are fitted exclusively
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Seamless integration of GEM, a density based-force field, for QM/MM simulations via LICHEM, Psi4, and Tinker-HP J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Jorge Nochebuena, Andrew C. Simmonett, G. Andrés Cisneros
Hybrid quantum mechanics/molecular mechanics (QM/MM) simulations have become an essential tool in computational chemistry, particularly for analyzing complex biological and condensed phase systems. Building on this foundation, our work presents a novel implementation of the Gaussian Electrostatic Model (GEM), a polarizable density-based force field, within the QM/MM framework. This advancement provides
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Energy decomposition analysis method using density matrix formulation J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Yueyang Zhang, Longxiang Yan, Wei Wu, Peifeng Su
In this work, an energy decomposition analysis (EDA) method with the strategy of density matrix, called DM-EDA, is proposed on the basis of single reference electronic structure calculations. Different from traditional EDA methods, instead of an intermediate state wave function, the EDA terms in DM-EDA are expressed in the forms of the density matrix. This method can be carried out with various kinds
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Rate theory of gas–liquid nucleation: Quest for the elusive quantitative accuracy J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Subhajit Acharya, Biman Bagchi
The task of a first principles theoretical calculation of the rate of gas–liquid nucleation has remained largely incomplete despite the existence of reliable results from unbiased simulation studies at large supersaturation. Although the classical nucleation theory formulated by Becker–Doring–Zeldovich about a century ago provides an elegant, widely used picture of nucleation in a first-order phase
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Bond-selective effect for the dissociative chemisorption of HOD on the Ni(100) surface revealed at the full-dimensional quantum dynamical level J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Tianhui Liu, Bina Fu, Dong H. Zhang
We present a comprehensive investigation into the dissociative chemisorption of HOD on a rigid Ni(100) surface using an approximate full-dimensional (9D) quantum dynamics approach, which was based on the time-dependent wave-packet calculations on a full-dimensional potential energy surface obtained through neural network fitting to density functional theory energy points. The approximate-9D probabilities
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Switch the click: Ultrafast photochemistry of photoDIBO-OH tracked by time-resolved IR spectroscopy J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 L. Denninger, H. Brunst, L. J. G. W. van Wilderen, M. Horz, H. M. A. Masood, C. D. McNitt, I. Burghardt, V. V. Popik, J. Bredenbeck
Click chemistry refers to selective reactions developed for grafting of bio(macro)molecules in their biological media. Caged click compounds have been employed to spatiotemporally control click reactions. Here, we survey the uncaging of photo-dibenzocyclooctyne-OH (photoDIBO-OH) to its click-chemistry active form DIBO-OH, with particular attention to its conversion timescale and efficiency. Ultraviolet
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Effects of carbon concentration on the local atomic structure of amorphous GST J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Robert J. Appleton, Zachary D. McClure, David P. Adams, Alejandro Strachan
Ge-Sb-Te (GST) alloys are leading phase-change materials for data storage due to the fast phase transition between amorphous and crystalline states. Ongoing research aims at improving the stability of the amorphous phase to improve retention. This can be accomplished by the introduction of carbon as a dopant to Ge2Sb2Te5, which is known to alter the short- and mid-range structure of the amorphous phase
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Prediction through quantum dynamics simulations: Photo-excited cyclobutanone J. Chem. Phys. (IF 4.4) Pub Date : 2024-05-01 Olivia Bennett, Antonia Freibert, K. Eryn Spinlove, Graham A. Worth
Quantum dynamics simulations are becoming a standard tool for simulating photo-excited molecular systems involving a manifold of coupled states, known as non-adiabatic dynamics. While these simulations have had many successes in explaining experiments and giving details of non-adiabatic transitions, the question remains as to their predictive power. In this work, we present a set of quantum dynamics
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Interactions of adsorbing cosolutes with hydrophobic hydration shells J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-30 Swaminath Bharadwaj, Madhusmita Tripathy, Nico F. A. van der Vegt
The analysis of water density fluctuations in the hydration shell of nonpolar solutes provides insights into water-mediated interactions, especially hydrophobic interactions. These fluctuations are sensitive to small perturbations due to changes in thermodynamic conditions, such as temperature and pressure, but also to the presence of cosolutes, such as salts or small organic molecules. Herein, we
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Interoperable workflows by exchanging grid-based data between quantum-chemical program packages J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-30 Kevin Focke, Matteo De Santis, Mario Wolter, Jessica A. Martinez B, Valérie Vallet, André Severo Pereira Gomes, Małgorzata Olejniczak, Christoph R. Jacob
Quantum-chemical subsystem and embedding methods require complex workflows that may involve multiple quantum-chemical program packages. Moreover, such workflows require the exchange of voluminous data that go beyond simple quantities, such as molecular structures and energies. Here, we describe our approach for addressing this interoperability challenge by exchanging electron densities and embedding
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Three-phase equilibria of hydrates from computer simulation. II. Finite-size effects in the carbon dioxide hydrate J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-30 J. Algaba, S. Blazquez, E. Feria, J. M. Míguez, M. M. Conde, F. J. Blas
In this work, the effects of finite size on the determination of the three-phase coexistence temperature (T3) of the carbon dioxide (CO2) hydrate have been studied by molecular dynamic simulations and using the direct coexistence technique. According to this technique, the three phases involved (hydrate–aqueous solution–liquid CO2) are placed together in the same simulation box. By varying the number
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The effect of microsolvation on the structure, nuclear quadrupole coupling, and internal rotation: The methyl carbamate⋯(H2O)1–3 complexes J. Chem. Phys. (IF 4.4) Pub Date : 2024-04-30 Pablo Pinacho, Juan Carlos López, Zbigniew Kisiel, Susana Blanco
Microsolvation of the carbamate moiety delivers precise information on complexation effects on the N–C=O backbone and is of relevance to the peptide bond functionality. In this context, the mono-, di-, and trihydrated complexes of methyl carbamate have been studied in molecular expansion by high-resolution microwave spectroscopy, using chirped-pulse and Fabry–Perot resonator Fourier transform microwave