TY - JOUR
T1 - Cut-off Scale and Complex Formation in Density Functional Theory Computations of Epoxy-Amine Reactivity
AU - Laurikainen, Pekka V.
AU - Sarlin, Essi L.
N1 - Funding Information:
P.V. Laurikainen received funding from the Tampere University Graduate School. E.L. Sarlin received funding from the Academy of Finland postdoctoral project “From micro—scale data to macro—scale understanding for improved safety of composite materials—MicMac” (grant no. 314983).
Publisher Copyright:
©
PY - 2021/11/9
Y1 - 2021/11/9
N2 - Most of the properties of epoxy resins are tied to their degree of cross-linking, making understanding the reactivity of different epoxy systems a crucial aspect of their utilization. Here, epoxy-amine reactivity is studied with density functional theory (DFT) at various cut-off levels to explore the suitability of the method for estimating the reactivity of specific epoxy systems. Although it is common to use minimal structures in DFT to reduce computational cost, the results of this study highlight the important role of hydrogen bonding and other noncovalent interactions in the reactivity. This is a promising result for differentiating the most probable reactive paths for different resin systems. The significance of amine groups as a potential source of catalyzing H-bonds was also explored and, while not quite as effective as a catalyst as a hydroxyl group, a clear catalyzing effect was observed in the transition state energies. Unfortunately, the added complexity of a more representative reactive system also results in increased computational cost, highlighting the need for proper selection of structural cutoffs.
AB - Most of the properties of epoxy resins are tied to their degree of cross-linking, making understanding the reactivity of different epoxy systems a crucial aspect of their utilization. Here, epoxy-amine reactivity is studied with density functional theory (DFT) at various cut-off levels to explore the suitability of the method for estimating the reactivity of specific epoxy systems. Although it is common to use minimal structures in DFT to reduce computational cost, the results of this study highlight the important role of hydrogen bonding and other noncovalent interactions in the reactivity. This is a promising result for differentiating the most probable reactive paths for different resin systems. The significance of amine groups as a potential source of catalyzing H-bonds was also explored and, while not quite as effective as a catalyst as a hydroxyl group, a clear catalyzing effect was observed in the transition state energies. Unfortunately, the added complexity of a more representative reactive system also results in increased computational cost, highlighting the need for proper selection of structural cutoffs.
U2 - 10.1021/acsomega.1c03229
DO - 10.1021/acsomega.1c03229
M3 - Article
AN - SCOPUS:85118980619
SN - 2470-1343
VL - 6
SP - 29424
EP - 29431
JO - ACS Omega
JF - ACS Omega
IS - 44
ER -