Mattia Perrone, Matteo Cioni, Massimo Delle Piane, Giovanni M Pavan
{"title":"Unsupervised tracking of local and collective defects dynamics in metals under deformation.","authors":"Mattia Perrone, Matteo Cioni, Massimo Delle Piane, Giovanni M Pavan","doi":"10.1063/5.0265378","DOIUrl":"https://doi.org/10.1063/5.0265378","url":null,"abstract":"<p><p>Metals owe their unique mechanical properties to how defects emerge and propagate within their crystal structure under stress. However, the mechanisms leading from the early emerging (local) defects to the amplification of dislocations (collective plastic events) are not easy to track. Here, using tensile-stress atomistic simulations of a copper lattice as a case study, we revisit this classical problem under a new perspective based on local dynamics rather than on purely structural arguments. We use a data-driven approach that allows tracking how local fluctuations emerge and accumulate in the atomic lattice in space and time, anticipating/determining the emergence of local or collective structural defects during deformation. Building solely on the general concepts of local fluctuations and spatiotemporal fluctuation correlations, this approach allows characterizing in a unique way the evolution through the elastic, plastic, and fracture phases, describing metals as complex systems where collective phenomena originate from local dynamical triggering events.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 21","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144225598","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kiriko Terai, Kelsey A Parker, Andrew J Smith, David N Beratan
{"title":"Hopping mediated transport between finite pools of redox proteins.","authors":"Kiriko Terai, Kelsey A Parker, Andrew J Smith, David N Beratan","doi":"10.1063/5.0267910","DOIUrl":"https://doi.org/10.1063/5.0267910","url":null,"abstract":"<p><p>Transport reactions in biology involve the flow of particles-electrons, ions, or molecules-between reservoirs. We explore how electron transport between finite reservoirs depends on the nature of the reservoirs, including their size, occupancy, and interactions. We compare the transport kinetics produced by narrowband and wideband infinite reservoir models (described earlier) with a finite narrowband reservoir model. The transport between finite reservoirs is found to depend on both the initial charge distribution and the number of carriers present. Whether or not a steady-state transport regime is accessed prior to reaching the equilibrium charge distribution depends on these initial conditions.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 21","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144225596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Stereoselectivity of cis-trans photoisomerization in ethylene: The significance of symmetry breaking minimum energy conical intersection.","authors":"Tengwei Chen, Huihui Deng, Wei Wu, Zhenhua Chen","doi":"10.1063/5.0271184","DOIUrl":"https://doi.org/10.1063/5.0271184","url":null,"abstract":"<p><p>This work finds that there are eight distinguished symmetry breaking minimum energy conical intersections (MECIs) between the N/V states of ethylene, in which the first four of them are closer to the reactant configuration than the remaining four. Consequently, the initially excited ethylene has a higher probability to relax to the first four MECIs or their adjacent configurations. Moreover, the ground potential energy surface around the first four MECIs has an asymmetric peaked topology and tilts toward the reactant configuration. Therefore, the cis-trans photoisomerization reaction in ethylene can exhibit the stereoselectivity of returning more back to the reactant rather than forming the product. In addition, the geometry-electronic structure relation and the geometric phase effect associated with a conical intersection were demonstrated by employing the adiabatic-to-diabatic analysis, in which the complete active space self-consistent-field wave function is represented by the equivalent covalent and ionic valence bond functions.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 21","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144225597","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhaofa Li, Jiawei Peng, Yifei Zhu, Chao Xu, Liang Peng, Maxim F Gelin, Feng Long Gu, Zhenggang Lan
{"title":"On-the-fly simulations of transient absorption pump-probe spectra: Combining mapping dynamics with doorway-window protocol.","authors":"Zhaofa Li, Jiawei Peng, Yifei Zhu, Chao Xu, Liang Peng, Maxim F Gelin, Feng Long Gu, Zhenggang Lan","doi":"10.1063/5.0252891","DOIUrl":"https://doi.org/10.1063/5.0252891","url":null,"abstract":"<p><p>We have constructed an ab initio protocol for the simulation of transient-absorption (TA) pump-probe (PP) signals of realistic polyatomic systems. The protocol is based on interfacing the doorway-window representation of spectroscopic signals with the on-the-fly mapping Hamiltonian dynamics approach at the symmetrical quasi-classical/Meyer-Miller level. The methodology is applied to the simulation of TA PP signals of two molecular systems, azobenzene and cis-hepta-3,5,7-trieniminium cation. For both molecules, the TA PP spectra were demonstrated to give a direct fingerprint of the excited state wavepacket dynamics and internal conversion, which permits the monitoring of the isomerization pathways en route to the final photoproducts.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 20","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144150524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Role of quantum corrections to the kinetic energy and three-body interactions on the thermodynamic properties of neon.","authors":"Ulrich K Deiters, Richard J Sadus","doi":"10.1063/5.0272013","DOIUrl":"https://doi.org/10.1063/5.0272013","url":null,"abstract":"<p><p>Molecular simulations are reported for the thermodynamic properties of Ne at temperatures between 30 and 300 K and pressures up to 100 MPa using an intermolecular potential that combines ab initio two-body, three-body, and quantum terms. Quantum corrections to the kinetic energy (QCKE) are also applied to the simulation data. Three-body interactions make important contributions to the pressure-volume-temperature behavior, enthalpy, heat capacity, isothermal compressibility, isochoric pressure coefficient, and isobaric thermal expansion coefficient of Ne. In particular, three-body interactions are required to correctly determine the volume and greatly improve the accuracy of enthalpy, isochoric pressure coefficient, and isobaric thermal expansion coefficient. QCKE also make an important contribution to the properties of Ne that has not been previously recognized. The addition of QCKE means that the caloric thermodynamic properties of Ne can often be determined a priori to an accuracy comparable to that of the reference data.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 20","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144187121","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Kinetics of phase transition in nonreciprocal mixtures of passive and chemophoretically active particles.","authors":"Manisha Jhajhria, Subir K Das, Snigdha Thakur","doi":"10.1063/5.0258020","DOIUrl":"https://doi.org/10.1063/5.0258020","url":null,"abstract":"<p><p>We study phase separation kinetics in two-dimensional binary mixtures of active and passive colloids. An active particle acts as a source of the chemical gradient to induce phoretic motion among the passive particles. Mediated by this effective interaction, the suspension undergoes separation resembling a vapor-liquid phase transition. Via simulations incorporating Langevin dynamics, we construct the related steady-state phase diagram. We exploit this knowledge to study structure and growth associated with kinetics following sudden quenches of homogeneous systems into the miscibility gap, for far-from-critical and near-critical densities. An advanced finite-size scaling technique is employed to calculate the growth exponents in the thermodynamically large system size limit, using data from systems of different finite sizes, for each of the cases. The growth data are described well by a recently constructed analytical function, irrespective of system size and particle density. Our results demonstrate enhancement in the growth exponent when the phoretic strength is increased. For the off-critical case, we have discussed the possible mechanism(s) in the background of an appropriate theoretical picture.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144110974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rui Bian, Zheng-Xuan Wang, Meng-Hui Wang, Zhong-Hua Cui
{"title":"Triply bonded C≡C characteristics between planar hypercoordinate carbons in a two-dimensional Be4C3 monolayer.","authors":"Rui Bian, Zheng-Xuan Wang, Meng-Hui Wang, Zhong-Hua Cui","doi":"10.1063/5.0264650","DOIUrl":"https://doi.org/10.1063/5.0264650","url":null,"abstract":"<p><p>We report the discovery of two 2D Be4C3 monolayers-o-Be4C3 and m-Be4C3-as the lowest-energy structures, each exhibiting unique planar hypercoordinate carbon bonding characteristics. Both monolayers feature a C≡C triply bonded motif formed between planar tetracoordinate carbon (ptC) and planar pentacoordinate carbon (ppC) centers, coordinating with three Be atoms in o-Be4C3 and four Be atoms in m-Be4C3. Bonding analysis reveals dual behavior: the p-orbital electrons in the C≡C bonds remain primarily localized, while other ptC atoms coordinated with four Be atoms exhibit fully delocalized electron density across the Be4C framework. This mainly localized π-bonding makes Be4C3 the first 2D material to feature multiply bonded planar hypercoordinate carbon motifs. Both monolayers demonstrate good thermodynamic and kinetic stability. Notably, o-Be4C3 possesses a small indirect bandgap, while m-Be4C3 exhibits 2D phonon-mediated superconductivity with a transition temperature (Tc) of 4.5 K, connecting \"anti-van't Hoff/Le Bel\" structures to promising applications in electronics and optoelectronics.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"From internal state variables to fluctuations in glass-forming materials: The linear dynamic heat capacity, expansivity, and compressibility.","authors":"Claudio Corbisieri","doi":"10.1063/5.0259276","DOIUrl":"https://doi.org/10.1063/5.0259276","url":null,"abstract":"<p><p>Several macroscopic-phenomenological theories exist that account for dissipative effects in the dynamic behavior of glass-forming materials. Thermodynamics with internal state variables, for example, provides a rationale for assessing the multiplicity of relaxation mechanisms observed in the linear dynamic heat capacity, expansivity, and compressibility. However, the convoluted formalism of these theories often obstructs the assessment of microscopic characteristics associated with material behavior that can otherwise be studied within linear response theory. In this work, we address this problem by deriving memory functionals of the entropy and volume from a set of ordinary differential equations posed by the normal-coordinate transform of the internal state variables. A generalized susceptibility matrix that represents the linear dynamic material behavior in the frequency domain is the result. In agreement with microscopic reversibility, the generalized susceptibility matrix and its time-domain transform are symmetric, thus substantiating the hypothesis of equal distribution of relaxation times in pressure-jump entropy relaxation and temperature-jump volume relaxation. The Prigogine-Defay ratio in terms of equilibrium fluctuations is obtained from the imaginary part of the generalized susceptibility matrix via the fluctuation-dissipation theorem. By combining fundamentals from classical irreversible thermodynamics and rational thermodynamics to derive the memory functionals, this work contributes to a theoretical framework for assessing macroscopic-phenomenological and microscopic characteristics of glass-forming materials associated with the linear dynamic heat capacity, expansivity, and compressibility. In addition, a compilation of the generalized susceptibility and its time-domain transform, both evaluated for the relaxation-time distributions that lead to the Debye, Kohlrausch, Cole-Cole, Davidson-Cole, and Havriliak-Negami relaxation functions, is provided.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Katrianna S Sarkar, Kevin A Interiano-Alberto, Jack F Douglas, Robert S Hoy
{"title":"Quantitative relations between nearest-neighbor persistence and slow heterogeneous dynamics in supercooled liquids.","authors":"Katrianna S Sarkar, Kevin A Interiano-Alberto, Jack F Douglas, Robert S Hoy","doi":"10.1063/5.0262404","DOIUrl":"https://doi.org/10.1063/5.0262404","url":null,"abstract":"<p><p>Using molecular dynamics simulations of a binary Lennard-Jones model of glass-forming liquids, we examine how the decay of the normalized neighbor-persistence function CB(t), which decays from unity at short times to zero at long times as particles lose the neighbors that were present in their original first coordination shell, compares with those of other, more conventionally utilized relaxation metrics. In the strongly non-Arrhenius temperature regime below the onset temperature TA, we find that CB(t) can be described using the same generic double-stretched-exponential functional form that is often utilized to fit the self-intermediate scattering function S(q, t) of glass-forming liquids in this regime. The ratio of the bond lifetime τbond associated with CB(t)'s slower decay mode to the α-relaxation time τα varies appreciably and non-monotonically with T, peaking at τbond/τα ≃ 45 at T ≃ Tx, where Tx is a crossover temperature separating the high- and low-temperature regimes of glass-formation. In contrast, τbond remains on the order of the overlap time τov (the time interval over which a typical particle moves by half its diameter), and the peak time τχ for the susceptibility χB(t) associated with the spatial heterogeneity of CB(t) remains on the order of τimm (the characteristic lifetime of immobile-particle clusters), even as each of these quantities varies by roughly 5 orders of magnitude over our studied range of T. Thus, we show that CB(t) and χB(t) provide semi-quantitative spatially-averaged measures of the slow heterogeneous dynamics associated with the persistence of immobile-particle clusters.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andrea García-Hernández, Ana Yañez-Aulestia, Salomón Cordero-Sánchez, J Marcos Esparza-Schulz, Ilich A Ibarra, Alejandro Martínez-Borquez, Víctor M Trejos
{"title":"Theoretical modeling of adsorption isotherms and isosteric heat of associating and non-associating fluids using the two-dimensional SAFT-VR Mie approach.","authors":"Andrea García-Hernández, Ana Yañez-Aulestia, Salomón Cordero-Sánchez, J Marcos Esparza-Schulz, Ilich A Ibarra, Alejandro Martínez-Borquez, Víctor M Trejos","doi":"10.1063/5.0263353","DOIUrl":"https://doi.org/10.1063/5.0263353","url":null,"abstract":"<p><p>In this work, the two-dimensional Statistical Associating Fluid Theory for fluids interacting via Mie pair potentials (2D-SAFT-VR Mie) is applied to model adsorption isotherms and isosteric heat of adsorption for both associating and non-associating fluids on solid surfaces. First, we derive analytical expressions for the first- and second-order perturbation terms of the Helmholtz free energy in the 2D system, based on the radial distribution function of a hard-disk system. Next, we develop an adsorption model that accounts for the interactions between the adsorbed and bulk phases, incorporating the Mie pair potential as a function of repulsive and attractive exponents. The theoretical approach is validated against Gibbs ensemble Monte Carlo simulations for the adsorption isotherms of associating and non-associating fluids, showing excellent agreement. Finally, the 2D-SAFT-VR Mie approach is applied to describe the adsorption isotherms and isosteric heat of adsorption of methane, nitrogen, carbon dioxide, sulfur dioxide, and water on carbonaceous materials, including dry activated carbon, zeolites, and metal-organic frameworks (MOFs). The energy depth of the surface-particle potential (ɛw) and the specific surface area (as) are free molecular parameters determined by fitting to experimental adsorption isotherms. The obtained ɛw and as values are consistent with the experimental values of isosteric heat of adsorption at zero coverage and Brunauer-Emmett-Teller surface area, respectively. In all cases, the calculated adsorption behavior exhibits excellent agreement with experimental data. These findings provide valuable theoretical insights into the design and optimization of efficient fluid storage, separation, and purification systems in complex materials.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093910","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}