We developed an explicit equation of state (EOS) for small non polar molecules by means of an effective two-body potential. The average effect of three-body forces was incorporated as a perturbation, which results in rescaled values for the parameters of the two-body potential. These values replace the original ones in the EOS corresponding to the two-body interaction. We applied this procedure to the heavier noble gases and used a modified Kihara function with an effective Axilrod-Teller-Muto (ATM) term to represent the two- and three-body forces. We also performed molecular dynamics simulations with two- and three-body forces. There was good agreement between predicted, simulated, and experimental thermodynamic properties of neon, argon, krypton, and xenon, up to twice the critical density and up to five times the critical temperature. In order to achieve 1% accuracy of the pressure at liquid densities, the EOS must incorporate the effect of ATM forces. The ATM factor in the rescaled two-body energy is most important at temperatures around and lower than the critical one. Nonetheless, the rescaling of two-body diameter cannot be neglected at liquid-like densities even at high temperature. This methodology can be extended straightforwardly to deal with other two- and three-body potentials. It could also be used for other nonpolar substances where a spherical two-body potential is still a reasonable coarse-grain approximation.
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http://dx.doi.org/10.1063/1.4829055 | DOI Listing |
J Phys Chem Lett
January 2025
Kenneth S. Pitzer Theory Center and Department of Chemistry, University of California, Berkeley, California 94720, United States.
This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion pairings. We find that all individual EDA terms remain well-approximated in the CMM for ion-water and ion-ion interactions, except for polarization, which shows errors due to the partial covalency of ion interactions near their equilibrium. We quantify the onset of the dative bonding regime by examining the change in molecular polarizability and Mayer bond indices as a function of distance, showing that partial covalency manifests by breaking the symmetry of atomic polarizabilities while strongly damping them at short-range.
View Article and Find Full Text PDFTransplant Proc
December 2024
Department of Human Anatomy, Medical School, Nanjing University, Nanjing, China; Jiangsu Key Laboratory of Molecular Medicine, Medical School, Nanjing University, Nanjing, China. Electronic address:
Background: In recent decades, China has experienced a shortage of donated bodies and organs for dissection during medical education and clinical transplantation. This study investigated and analyzed motivational factors affecting body and organ donation in China.
Methodology: Thirty-three body and organ donation volunteers were interviewed in-depth, and their donation motivations were investigated.
J Chem Theory Comput
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Laboratory of Molecular Modeling and Design, State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
The computational complexity of quantum chemistry methods has prompted the development of reactive force fields, facilitating practical applications of molecular dynamics simulations for large-scale reactive systems. Current reactive force fields typically employ intricate corrections based on prior chemical knowledge, which severely impedes their further advancement. This study presents a new atomic multipole-based reactive model with bond free (OPERATOR).
View Article and Find Full Text PDFJ Chem Theory Comput
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Department of Mechanical and Industrial Engineering, University of Illinois, Chicago, Illinois 60607, United States.
A wide array of models, spanning from computationally expensive ab initio methods to a spectrum of force-field approaches, have been developed and employed to probe silica polymorphs and understand growth processes and atomic-level dynamical transitions in silica. However, the quest for a model capable of making accurate predictions with high computational efficiency for various silica polymorphs is still ongoing. Recent developments in short-range machine-learned models, such as GAP and NNPScan, have shown promise in providing reasonable descriptions of silica, but their computational cost remains high compared to force fields such as BKS which are based on simple interpretable functional forms.
View Article and Find Full Text PDFJ Phys Chem Lett
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Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, China.
RDX undergoes pressures of approximately 30-50 GPa during detonation, leading to significant changes in intermolecular interactions. Accurately describing these interactions is crucial for understanding the energy transfer in the detonation process. To address this, this work introduces a many-body expansion-based quantum mechanical force field (MB-QMFF) to accurately describe RDX's intermolecular interactions under high pressures.
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