A multi-scale Monte Carlo method for electrolytes
Artifacts arise in the simulations of electrolytes using periodic boundary conditions (PBCs). We show the origin of these artifacts are the periodic image charges and the constraint of charge neutrality inside the simulation box, both of which are unphysical from the view point of real systems. To c...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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IOP Publishing
2015-01-01
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| Series: | New Journal of Physics |
| Subjects: | |
| Online Access: | https://doi.org/10.1088/1367-2630/17/8/083062 |
| _version_ | 1797751071519539200 |
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| author | Yihao Liang Zhenli Xu Xiangjun Xing |
| author_facet | Yihao Liang Zhenli Xu Xiangjun Xing |
| author_sort | Yihao Liang |
| collection | DOAJ |
| description | Artifacts arise in the simulations of electrolytes using periodic boundary conditions (PBCs). We show the origin of these artifacts are the periodic image charges and the constraint of charge neutrality inside the simulation box, both of which are unphysical from the view point of real systems. To cure these problems, we introduce a multi-scale Monte Carlo (MC) method, where ions inside a spherical cavity are simulated explicitly, while ions outside are treated implicitly using a continuum theory. Using the method of Debye charging, we explicitly derive the effective interactions between ions inside the cavity, arising due to the fluctuations of ions outside. We find that these effective interactions consist of two types: (1) a constant cavity potential due to the asymmetry of the electrolyte, and (2) a reaction potential that depends on the positions of all ions inside. Combining the grand canonical Monte Carlo (GCMC) with a recently developed fast algorithm based on image charge method, we perform a multi-scale MC simulation of symmetric electrolytes, and compare it with other simulation methods, including PBC + GCMC method, as well as large scale MC simulation. We demonstrate that our multi-scale MC method is capable of capturing the correct physics of a large system using a small scale simulation. |
| first_indexed | 2024-03-12T16:43:01Z |
| format | Article |
| id | doaj.art-e7b0116a3ba94e54be06d6831e6ed5c2 |
| institution | Directory Open Access Journal |
| issn | 1367-2630 |
| language | English |
| last_indexed | 2024-03-12T16:43:01Z |
| publishDate | 2015-01-01 |
| publisher | IOP Publishing |
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| series | New Journal of Physics |
| spelling | doaj.art-e7b0116a3ba94e54be06d6831e6ed5c22023-08-08T14:23:33ZengIOP PublishingNew Journal of Physics1367-26302015-01-0117808306210.1088/1367-2630/17/8/083062A multi-scale Monte Carlo method for electrolytesYihao Liang0Zhenli Xu1Xiangjun Xing2Department of Physics and Astronomy , Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of ChinaInstitute of Natural Sciences , Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of China; Department of Mathematics , and MOE Key Lab of Scientific and Engineering Computing, Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of ChinaDepartment of Physics and Astronomy , Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of China; Institute of Natural Sciences , Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of China; Collaborative Innovation Center of Advanced Microstructures , Nanjing 210093, People's Republic of ChinaArtifacts arise in the simulations of electrolytes using periodic boundary conditions (PBCs). We show the origin of these artifacts are the periodic image charges and the constraint of charge neutrality inside the simulation box, both of which are unphysical from the view point of real systems. To cure these problems, we introduce a multi-scale Monte Carlo (MC) method, where ions inside a spherical cavity are simulated explicitly, while ions outside are treated implicitly using a continuum theory. Using the method of Debye charging, we explicitly derive the effective interactions between ions inside the cavity, arising due to the fluctuations of ions outside. We find that these effective interactions consist of two types: (1) a constant cavity potential due to the asymmetry of the electrolyte, and (2) a reaction potential that depends on the positions of all ions inside. Combining the grand canonical Monte Carlo (GCMC) with a recently developed fast algorithm based on image charge method, we perform a multi-scale MC simulation of symmetric electrolytes, and compare it with other simulation methods, including PBC + GCMC method, as well as large scale MC simulation. We demonstrate that our multi-scale MC method is capable of capturing the correct physics of a large system using a small scale simulation.https://doi.org/10.1088/1367-2630/17/8/083062electrolytesMonte Carlomulti-scaleimage charges |
| spellingShingle | Yihao Liang Zhenli Xu Xiangjun Xing A multi-scale Monte Carlo method for electrolytes New Journal of Physics electrolytes Monte Carlo multi-scale image charges |
| title | A multi-scale Monte Carlo method for electrolytes |
| title_full | A multi-scale Monte Carlo method for electrolytes |
| title_fullStr | A multi-scale Monte Carlo method for electrolytes |
| title_full_unstemmed | A multi-scale Monte Carlo method for electrolytes |
| title_short | A multi-scale Monte Carlo method for electrolytes |
| title_sort | multi scale monte carlo method for electrolytes |
| topic | electrolytes Monte Carlo multi-scale image charges |
| url | https://doi.org/10.1088/1367-2630/17/8/083062 |
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