Analysis of nucleation using mean first-passage time data from molecular dynamics simulation
We introduce a method for the analysis of nucleation using mean first-passage time (MFPT) statistics obtained by molecular dynamics simulation. The method is based on the Becker-Döring model for the dynamics of a nucleation-mediated phase change and rigorously accounts for the system size dependence...
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| Format: | Article |
| Language: | en_US |
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American Institute of Physics (AIP)
2017
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| Online Access: | http://hdl.handle.net/1721.1/109705 https://orcid.org/0000-0002-9693-5219 https://orcid.org/0000-0001-8137-1732 |
| _version_ | 1811088211509772288 |
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| author | Nicholson, David Andrew Rutledge, Gregory C |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Nicholson, David Andrew Rutledge, Gregory C |
| author_sort | Nicholson, David Andrew |
| collection | MIT |
| description | We introduce a method for the analysis of nucleation using mean first-passage time (MFPT) statistics obtained by molecular dynamics simulation. The method is based on the Becker-Döring model for the dynamics of a nucleation-mediated phase change and rigorously accounts for the system size dependence of first-passage statistics. It is thus suitable for the analysis of systems in which the separation between time scales for nucleation and growth is small, due to either a small free energy barrier or a large system size. The method is made computationally practical by an approximation of the first-passage time distribution based on its cumulant expansion. Using this approximation, the MFPT of the model can be fit to data from molecular dynamics simulation in order to estimate valuable kinetic parameters, including the free energy barrier, critical nucleus size, and monomer attachment pre-factor, as well as the steady-state rates of nucleation and growth. The method is demonstrated using a case study on nucleation of n-eicosane crystals from the melt. For this system, we found that the observed distribution of first-passage times do not follow an exponential distribution at short times, rendering it incompatible with the assumptions made by some other methods. Using our method, the observed distribution of first-passage times was accurately described, and reasonable estimates for the kinetic parameters and steady-state rates of nucleation and growth were obtained. |
| first_indexed | 2024-09-23T13:58:01Z |
| format | Article |
| id | mit-1721.1/109705 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:58:01Z |
| publishDate | 2017 |
| publisher | American Institute of Physics (AIP) |
| record_format | dspace |
| spelling | mit-1721.1/1097052022-10-01T18:19:13Z Analysis of nucleation using mean first-passage time data from molecular dynamics simulation Nicholson, David Andrew Rutledge, Gregory C Massachusetts Institute of Technology. Department of Chemical Engineering Nicholson, David Andrew Rutledge, Gregory C We introduce a method for the analysis of nucleation using mean first-passage time (MFPT) statistics obtained by molecular dynamics simulation. The method is based on the Becker-Döring model for the dynamics of a nucleation-mediated phase change and rigorously accounts for the system size dependence of first-passage statistics. It is thus suitable for the analysis of systems in which the separation between time scales for nucleation and growth is small, due to either a small free energy barrier or a large system size. The method is made computationally practical by an approximation of the first-passage time distribution based on its cumulant expansion. Using this approximation, the MFPT of the model can be fit to data from molecular dynamics simulation in order to estimate valuable kinetic parameters, including the free energy barrier, critical nucleus size, and monomer attachment pre-factor, as well as the steady-state rates of nucleation and growth. The method is demonstrated using a case study on nucleation of n-eicosane crystals from the melt. For this system, we found that the observed distribution of first-passage times do not follow an exponential distribution at short times, rendering it incompatible with the assumptions made by some other methods. Using our method, the observed distribution of first-passage times was accurately described, and reasonable estimates for the kinetic parameters and steady-state rates of nucleation and growth were obtained. 2017-06-07T15:21:08Z 2017-06-07T15:21:08Z 2016-04 2016-02 Article http://purl.org/eprint/type/JournalArticle 0021-9606 1089-7690 http://hdl.handle.net/1721.1/109705 Nicholson, David A. and Rutledge, Gregory C. “Analysis of Nucleation Using Mean First-Passage Time Data from Molecular Dynamics Simulation.” The Journal of Chemical Physics 144, no. 13 (April 2016): 134105 © 2016 American Institute of Physics (AIP) https://orcid.org/0000-0002-9693-5219 https://orcid.org/0000-0001-8137-1732 en_US http://dx.doi.org/10.1063/1.4945256 Journal of Chemical Physics Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Institute of Physics (AIP) MIT Web Domain |
| spellingShingle | Nicholson, David Andrew Rutledge, Gregory C Analysis of nucleation using mean first-passage time data from molecular dynamics simulation |
| title | Analysis of nucleation using mean first-passage time data from molecular dynamics simulation |
| title_full | Analysis of nucleation using mean first-passage time data from molecular dynamics simulation |
| title_fullStr | Analysis of nucleation using mean first-passage time data from molecular dynamics simulation |
| title_full_unstemmed | Analysis of nucleation using mean first-passage time data from molecular dynamics simulation |
| title_short | Analysis of nucleation using mean first-passage time data from molecular dynamics simulation |
| title_sort | analysis of nucleation using mean first passage time data from molecular dynamics simulation |
| url | http://hdl.handle.net/1721.1/109705 https://orcid.org/0000-0002-9693-5219 https://orcid.org/0000-0001-8137-1732 |
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