Extended ensemble molecular dynamics method for constant strain rate uniaxial deformation of polymer systems
Open accessAbstract
We describe a novel molecular dynamics (MD) method to simulate the uniaxial deformation of an amorphous polymer. This method is based on a rigorously defined statistical mechanics ensemble appropriate for describing an isothermal, displacement controlled, uniaxial stress mechanical test. The total number of particles is fixed and the normal stresses in the direction normal to the applied strain are constant, i.e., an NTLxσyyσzz ensemble. By using the Lagrangian of the extended system (i.e., including additional variables corresponding to the temperature and cross-sectional area fluctuations), we derive a set of equations of motion for the atomic coordinates and the additional variables appropriate to this ensemble. In order to avoid the short MD time step appropriate for the stiff covalent bonds along the polymer chains, we introduce bond length constraints. This is achieved using a variation of the commonly used SHAKE [J. P. Ryckaert, G. Ciccotti, and H. J. C. Berendsen, J. Comp. Phys. 23, 327 (1977)] algorithm. A numerical method for integrating the equations of motion with constraints via a modification of the velocity Verlet [W. C. Swope, H. C. Andersen, P. H. Berens, and K. R. Wilson, J. Chem. Phys. 76, 637 (1982)] algorithm is presented. We apply this new algorithm to the constant strain rate deformation of an amorphous polyethylene in a model containing several distinct polymer chains. To our knowledge, this is the first time that bond length constraints were applied to a macromolecular system together with an extended ensemble in which the simulation cell shape is allowed to fluctuate.
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MD is a useful tool to qualitatively investigate the relationship between micro-scale phenomena and macro-scale mechanical properties and, to some extent, to quantitatively determine these terms.
“These previous results indicate that MD is a useful tool to qualitatively investigate the relationship between micro-scale phenomena and macro-scale mechanical properties and, to some extent, to quantitatively determine these terms.”
The united-atom approach simplifies each CH2 monomer as a single monomer particle and has been used by several researchers.
“This approach simplifies each CH2 monomer as a single monomer particle and has been used by several researchers [2][3][4].”
The simulated yield stress is the same order of magnitude as found in other simulations.
“This is the same order of magnitude as found in other simulations, for instance [2][3][4].”
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- Authors
- Yang, L., Srolovitz, D. J., & Yee, A. F.
- Affiliations
- University of Michigan (US)
- Venue
- The Journal of Chemical Physics
- Publisher
- AIP Publishing
- Published
- 1997-09-15
- Volume
- 107
- Issue
- 11
- Pages
- 4396-4407
- ISSN
- 0021-9606 (ISSN-L)
- 1089-7690
- OpenAlex
- W1978490881
- Cited by
- 56
- References
- 16
- Citations by year
- 2025: 3 · 2021: 2 · 2020: 1 · 2019: 3 · 2018: 3 · 2017: 2 · 2015: 1 · 2014: 1 · 2013: 3 · 2012: 1
- FWCI
- 1.87
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- The Journal of Chemical Physics (publishedVersion)
- Deep Blue (University of Michigan) (submittedVersion)
- APS March Meeting Abstracts
- Funders
- National Science Foundation
- Division of Materials Research
- Topics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Advanced Physical and Chemical Molecular Interactions
- Physical Sciences › Materials Science › Materials Chemistry › Material Dynamics and Properties
- Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Rheology and Fluid Dynamics Studies
- Keywords
- constant strain rate deformation, uniaxial deformation, amorphous polymers, velocity Verlet algorithm, polyethylene, macromolecular dynamics
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