Recent coarse-grained (CG) models have often supplemented conventional pair potentials with potentials that depend upon the local density around each particle. In this work, we investigate the temperature-dependence of these local density (LD) potentials. Specifically, we employ the multiscale coarse-graining (MS-CG) force-matching variational principle to parameterize pair and LD potentials for one-site CG models of molecular liquids at ambient pressure. The accuracy of these MS-CG LD potentials quite sensitively depends upon the length-scale, rc, that is employed to define the local density. When the local density is defined by the optimal length-scale, rc*, the MS-CG potential often accurately describes the reference state point and can provide reasonable transferability across a rather wide range of temperatures. At ambient pressure, the optimal LD length-scale varies linearly with temperature over a very wide range of temperatures. Moreover, if one adopts this temperature-dependent LD length-scale, then the MS-CG LD potential appears independent of temperature, while the MS-CG pair potential varies linearly across this temperature range. This provides a simple means for predicting pair and LD potentials that accurately model new state points without performing additional atomistic simulations. Surprisingly, at certain state points, the predicted potentials provide greater accuracy than MS-CG potentials that were optimized for the state point.
more »
« less
Investigating the energetic and entropic components of effective potentials across a glass transition
By eliminating unnecessary details, coarse-grained (CG) models provide the necessary efficiency for simulating scales that are inaccessible to higher resolution models. However, because they average over atomic details, the effective potentials governing CG degrees of freedom necessarily incorporate significant entropic contributions, which limit their transferability and complicate the treatment of thermodynamic properties. This work employs a dual-potential approach to consider the energetic and entropic contributions to effective interaction potentials for CG models. Specifically, we consider one- and three-site CG models for ortho-terphenyl (OTP) both above and below its glass transition. We employ the multiscale coarse-graining (MS-CG) variational principle to determine interaction potentials that accurately reproduce the structural properties of an all-atom (AA) model for OTP at each state point. We employ an energy-matching variational principle to determine an energy operator that accurately reproduces the intra- and inter-molecular energy of the AA model. While the MS-CG pair potentials are almost purely repulsive, the corresponding pair energy functions feature a pronounced minima that corresponds to contacting benzene rings. These energetic functions then determine an estimate for the entropic component of the MS-CG interaction potentials. These entropic functions accurately predict the MS-CG pair potentials across a wide range of liquid state points at constant density. Moreover, the entropic functions also predict pair potentials that quite accurately model the AA pair structure below the glass transition. Thus, the dual-potential approach appears a promising approach for modeling AA energetics, as well as for predicting the temperature-dependence of CG effective potentials.
more » « less- Award ID(s):
- 1856337
- NSF-PAR ID:
- 10361784
- Publisher / Repository:
- IOP Publishing
- Date Published:
- Journal Name:
- Journal of Physics: Condensed Matter
- Volume:
- 33
- Issue:
- 15
- ISSN:
- 0953-8984
- Page Range / eLocation ID:
- Article No. 154004
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
We investigate the temperature- and density-dependence of effective pair potentials for 1-site coarse-grained (CG) models of two industrial solvents, 1,4-dioxane and tetrahydrofuran. We observe that the calculated pair potentials are much more sensitive to density than to temperature. The generalized-Yvon-Born−Green framework reveals that this striking density-dependence reflects corresponding variations in the many-body correlations that determine the environment-mediated indirect contribution to the pair mean force. Moreover, we demonstrate, perhaps surprisingly, that this density-dependence is not important for accurately modeling the intermolecular structure. Accordingly, we adopt a density-independent interaction potential and transfer the density-dependence of the calculated pair potentials into a configuration- independent volume potential. Furthermore, we develop a single global potential that accurately models the intermolecular structure and pressure−volume equation of state across a very wide range of liquid state points. Consequently, this work provides fundamental insight into the density-dependence of effective pair potentials and also provides a significant step toward developing predictive CG models for efficiently modeling industrial solvents.more » « less
-
By averaging over atomic details, coarse-grained (CG) models provide profound computational and conceptual advantages for studying soft materials. In particular, bottom-up approaches develop CG models based upon information obtained from atomically detailed models. At least in principle, a bottom-up model can reproduce all the properties of an atomically detailed model that are observable at the resolution of the CG model. Historically, bottom-up approaches have accurately modeled the structure of liquids, polymers, and other amorphous soft materials, but have provided lower structural fidelity for more complex biomolecular systems. Moreover, they have also been plagued by unpredictable transferability and a poor description of thermodynamic properties. Fortunately, recent studies have reported dramatic advances in addressing these prior limitations. This Perspective reviews this remarkable progress, while focusing on its foundation in the basic theory of coarse-graining. In particular, we describe recent insights and advances for treating the CG mapping, for modeling many-body interactions, for addressing the state-point dependence of effective potentials, and even for reproducing atomic observables that are beyond the resolution of the CG model. We also outline outstanding challenges and promising directions in the field. We anticipate that the synthesis of rigorous theory and modern computational tools will result in practical bottom-up methods that not only are accurate and transferable but also provide predictive insight for complex systems.more » « less
-
Low resolution coarse-grained (CG) models provide remarkable com- putational and conceptual advantages for simulating soft materials. In principle, bottom-up CG models can reproduce all structural and thermodynamic properties of atomically detailed models that can be observed at the resolution of the CG model. This review discusses recent progress in developing theory and computational methods for achieving this promise. We first briefly review variational approaches for parameterizing interaction potentials and their relationship to ma- chine learning methods. We then discuss recent approaches for si- multaneously improving both the transferability and thermodynamic properties of bottom-up models by rigorously addressing the density- and temperature-dependence of these potentials. We also briefly dis- cuss exciting progress in modeling high resolution observables with low- resolution CG models. More generally, we highlight the essential role of the bottom-up framework not only for fundamentally understand- ing the limitations of prior CG models, but also for developing robust computational methods that resolve these limitations in practice.more » « less
-
The integral equation coarse-graining (IECG) approach is a promising high-level coarse-graining (CG) method for polymer melts, with variable resolution from soft spheres to multi CG sites, which preserves the structural and thermodynamical consistencies with the related atomistic simulations. When compared to the atomistic description, the procedure of coarse-graining results in smoother free energy surfaces, longer-ranged potentials, a decrease in the number of interaction sites for a given polymer, and more. Because these changes have competing effects on the computational efficiency of the CG model, care needs to be taken when studying the effect of coarse-graining on the computational speed-up in CG molecular dynamics simulations. For instance, treatment of long-range CG interactions requires the selection of cutoff distances that include the attractive part of the effective CG potential and force. In particular, we show how the complex nature of the range and curvature of the effective CG potential, the selection of a suitable CG timestep, the choice of the cutoff distance, the molecular dynamics algorithms, and the smoothness of the CG free energy surface affect the efficiency of IECG simulations. By direct comparison with the atomistic simulations of relatively short chain polymer melts, we find that the overall computational efficiency is highest for the highest level of CG (soft spheres), with an overall improvement of the computational efficiency being about 10 6 –10 8 for various CG levels/resolutions. Therefore, the IECG method can have important applications in molecular dynamics simulations of polymeric systems. Finally, making use of the standard spatial decomposition algorithm, the parallel scalability of the IECG simulations for various levels of CG is presented. Optimal parallel scaling is observed for a reasonably large number of processors. Although this study is performed using the IECG approach, its results on the relation between the level of CG and the computational efficiency are general and apply to any properly-constructed CG model.more » « less
