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Solution-Phase Conformational/Vibrational Anharmonicity in Comonomer Incorporation Polyolefin Catalysis

Lawniczak, James J. and Zhang, Xinglong and Christianson, Matthew and Bailey, Brad and Bremer, Sean and Barcia, Sarah and Mukhopadhyay, Sukrit and Klosin, Jerzy and Miller, Thomas F., III (2022) Solution-Phase Conformational/Vibrational Anharmonicity in Comonomer Incorporation Polyolefin Catalysis. Journal of Physical Chemistry A, 126 (39). pp. 6858-6869. ISSN 1089-5639. doi:10.1021/acs.jpca.2c04038. https://resolver.caltech.edu/CaltechAUTHORS:20221011-128968500.22

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Abstract

The prediction of comonomer incorporation statistics in polyolefin catalysis necessitates an accurate calculation of free energies corresponding to monomer binding and insertion, often requiring sub-kcal/mol resolution to resolve experimental free energies. Batch reactor experiments are used to probe incorporation statistics of ethene and larger α-olefins for three constrained geometry complexes which are employed as model systems. Herein, over 6 ns of quantum mechanics/molecular mechanics (QM/MM) molecular dynamics is performed in combination with the zero-temperature string method to characterize the solution-phase insertion barrier and to analyze the contributions from conformational and vibrational anharmonicity arising both in vacuum and in solution. Conformational sampling in the solution-phase results in 0–2 kcal/mol corrections to the insertion barrier which are on the same scale necessary to resolve experimental free energies. Anharmonic contributions from conformational sampling in the solution phase are crucial energy contributions missing from static density functional theory calculations and implicit solvation models, and the accurate calculation of these contributions is a key step toward the quantitative prediction of comonomer incorporation statistics.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpca.2c04038DOIArticle
ORCID:
AuthorORCID
Lawniczak, James J.0000-0003-1898-9809
Zhang, Xinglong0000-0003-1698-692X
Christianson, Matthew0000-0003-2889-0335
Klosin, Jerzy0000-0002-9045-7308
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:We acknowledge Peter Margl for his support in this project. This work was carried out with financial support from the University Partnership Initiative from the Dow Chemical Company. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under grant no. DGE-1144469. The computations presented here were conducted in the Resnick High Performance Center, a facility supported by the Resnick Sustainability Institute at the California Institute of Technology. X.Z. acknowledges the Agency for Science, Technology and Research (A*STAR), Singapore, for a National Science Scholarship.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
NSF Graduate Research FellowshipDGE-1144469
Dow Chemical CompanyUNSPECIFIED
Issue or Number:39
DOI:10.1021/acs.jpca.2c04038
Record Number:CaltechAUTHORS:20221011-128968500.22
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20221011-128968500.22
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:117360
Collection:CaltechAUTHORS
Deposited By: Research Services Depository
Deposited On:12 Oct 2022 22:33
Last Modified:12 Oct 2022 22:33

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