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Coil-to-Globule Transition in Polymeric Solvents

Xu, Yuci and Wang, Zhen-Gang (2021) Coil-to-Globule Transition in Polymeric Solvents. Macromolecules, 54 (23). pp. 10984-10993. ISSN 0024-9297. doi:10.1021/acs.macromol.1c01748.

[img] PDF (SCFT; comparison between the exact result and our approximation for the ideal Gaussian chain; radial density profiles of the globule; effect of the spring on the free energy of the globule; effect of the spring constant ...) - Supplemental Material
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We study the coil-to-globule (C–G) transition of a test polymer of chain length N1 in a polymeric solvent of chain length N using the self-consistent field theory. For short-chain solvents, the C–G transition point is given by (χN)_(tr)–1/2 ∼ (pN)^(3/4)N₁^(–1/2), consistent with an extended Lifshitz theory, where p = b²/v_m^(2/3) is the stiffness parameter. However, for long-chain solvents, the C–G transition becomes strongly first order, with the transition point given by (χN)_(tr)–1/2 ∼ pNN₁^(–2/3). A scaling analysis suggests that the transition point for any chain length combination is a universal function of the scaling variable x ≡ (pN)^(3/2)/N₁, which has the clear interpretation as the ratio between the pervaded volume of the solvent chain and the physical volume of the test chain and that a crossover between the two transition scenarios occurs at x ∼ 1. Furthermore, when properly nondimensionalized, the density profile in the globule state and the center density and the interfacial thickness of the globule at the transition also exhibit universal behavior. For both the short-chain and long-chain solvent cases, the C–G transition corresponds to the point when the interfacial thickness of the globule becomes comparable to the core size.

Item Type:Article
Related URLs:
URLURL TypeDescription
Xu, Yuci0000-0001-5163-2807
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2021 American Chemical Society. Received 19 August 2021. Revised 1 November 2021. Published online 17 November 2021. Y.X. gratefully acknowledges the funding support from the National Natural Science Foundation of China (grants 21973051) and the Chinese Scholarship Council. Z.-G.W. acknowledges the financial support from the Hong Kong Quantum AI Lab Ltd. The authors declare no competing financial interest.
Funding AgencyGrant Number
National Natural Science Foundation of China21973051
China Scholarship CouncilUNSPECIFIED
Hong Kong Quantum AI Lab Ltd.UNSPECIFIED
Subject Keywords:Thickness, Free energy, Solvents, Phase transitions, Polymers
Issue or Number:23
Record Number:CaltechAUTHORS:20211201-231208714
Persistent URL:
Official Citation:Coil-to-Globule Transition in Polymeric Solvents. Yuci Xu and Zhen-Gang Wang. Macromolecules 2021 54 (23), 10984-10993; DOI: 10.1021/acs.macromol.1c01748
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112152
Deposited By: George Porter
Deposited On:02 Dec 2021 20:51
Last Modified:15 Dec 2021 18:57

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