TY - JOUR

T1 - Structural Anomaly in Glasses: Molecular Dynamics Study of Organic Radical in Dibutylphthalate at Different Temperatures

AU - Alimov, Dmitry V.

AU - Ivanov, Mikhail Yu

AU - Pylaeva, Svetlana

AU - Fedin, Matvey V.

N1 - Funding Information: This work was supported by the Russian Science Foundation (grant No. 19-13-00071-Π, M.Y.I. and M.V.F., comparative analysis of MD and EPR data). S.P. acknowledges the DFG for funding (PY 117/1-1, 468786575). Publisher Copyright: © 2022 by the authors.

PY - 2022/12

Y1 - 2022/12

N2 - Understanding the heterogeneous nano/microscopic structures of various organic glasses is fundamental and necessary for many applications. Recently, unusual structural phenomena have been observed experimentally in various organic glasses near their glass transition temperatures ((Formula presented.)), including dibutyl phthalate (DBP). In particular, the librational motion of radical probe in the glass is progressively suppressed upon temperature increase. In this work, we report in-depth molecular dynamics studies of structural anomalies in DBP glass, that revealed insights into the general mechanism of these phenomena. In particular, we have evidenced that the two types of solvation within alkyl chains coexist, allowing only small-angle wobbling of the solute molecule (TEMPO radical), and another favouring large-angle rotations. The former solvation assumes constrained location of the solute near carboxyl groups of DBP, while the latter is coupled to the concerted movement of butyl chains. Remarkably, excellent qualitative and quantitative agreement with previous experimental results were obtained. As such, we are certain that the above-mentioned dynamic phenomena explain the intriguing structural anomalies observed in DBP and some other glasses in the vicinity of (Formula presented.).

AB - Understanding the heterogeneous nano/microscopic structures of various organic glasses is fundamental and necessary for many applications. Recently, unusual structural phenomena have been observed experimentally in various organic glasses near their glass transition temperatures ((Formula presented.)), including dibutyl phthalate (DBP). In particular, the librational motion of radical probe in the glass is progressively suppressed upon temperature increase. In this work, we report in-depth molecular dynamics studies of structural anomalies in DBP glass, that revealed insights into the general mechanism of these phenomena. In particular, we have evidenced that the two types of solvation within alkyl chains coexist, allowing only small-angle wobbling of the solute molecule (TEMPO radical), and another favouring large-angle rotations. The former solvation assumes constrained location of the solute near carboxyl groups of DBP, while the latter is coupled to the concerted movement of butyl chains. Remarkably, excellent qualitative and quantitative agreement with previous experimental results were obtained. As such, we are certain that the above-mentioned dynamic phenomena explain the intriguing structural anomalies observed in DBP and some other glasses in the vicinity of (Formula presented.).

KW - EPR

KW - glasses

KW - molecular dynamics

KW - Temperature

KW - Dibutyl Phthalate

KW - Glass/chemistry

KW - Transition Temperature

KW - Molecular Dynamics Simulation

UR - http://www.scopus.com/inward/record.url?scp=85143770831&partnerID=8YFLogxK

U2 - 10.3390/ijms232314859

DO - 10.3390/ijms232314859

M3 - Article

C2 - 36499187

AN - SCOPUS:85143770831

VL - 23

JO - International Journal of Molecular Sciences

JF - International Journal of Molecular Sciences

SN - 1661-6596

IS - 23

M1 - 14859

ER -