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The minute sample amount (\u22485\u00a0ng) required for FSC allows for the realization of cooling rates up to 50\u00a0000\u00a0K\u00a0s<jats:sup>\u22121<\/jats:sup> and to quench the sample into the amorphous state. By subsequent annealing at varying temperatures <jats:italic>T<\/jats:italic><jats:sub>a<\/jats:sub> and times <jats:italic>t<\/jats:italic><jats:sub>a<\/jats:sub> enthalpy relaxation, (homogeneous) nucleation and crystallization can be monitored with high precision. Determining the difference IR spectra between a quenched and an annealed sample unravels the development of the intra\u2010 and inter\u2010molecular interactions in detail; i) as first response taking place during enthalpy relaxation, the far reaching Coulomb interactions between the polar carbonyl\u00a0(C\u00a0\u2550\u00a0O) moieties are active; ii) in contrast, the methylene unit (CH<jats:sub>2<\/jats:sub>) and the aromatic ring show a response only, if homogeneous nucleation sets in, while the ester\u00a0(COC) moiety remains uninfluenced; iii) a hierarchy is observed in of the response of the different molecular moieties; iv) if crystallization comes to play, all molecular units are involved. The results are compared with recently published findings for polyamide 66 demonstrating the high molecular specificity of homogeneous nucleation and crystallization.<\/jats:p>","DOI":"10.1002\/macp.202200443","type":"journal-article","created":{"date-parts":[[2023,4,1]],"date-time":"2023-04-01T09:53:11Z","timestamp":1680342791000},"update-policy":"http:\/\/dx.doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["The Initial Molecular Interactions in the Course of Enthalpy Relaxation and Nucleation in Polyethylene Terephthalate (PET) as Monitored by Combined Nanocalorimetry and FTIR Spectroscopy"],"prefix":"10.1002","volume":"224","author":[{"ORCID":"http:\/\/orcid.org\/0000-0003-0643-7716","authenticated-orcid":false,"given":"Wycliffe Kiprop","family":"Kipnusu","sequence":"first","affiliation":[{"name":"Peter Debye Institute for Soft Matter Physics Leipzig University  Linnestr. 5 04103 Leipzig Germany"}]},{"given":"Evgeny","family":"Zhuravlev","sequence":"additional","affiliation":[{"name":"Institute of Physics University of Rostock  Albert\u2010Einstein str. 23\u201024 18051 Rostock Germany"}]},{"given":"Christoph","family":"Schick","sequence":"additional","affiliation":[{"name":"Institute of Physics University of Rostock  Albert\u2010Einstein str. 23\u201024 18051 Rostock Germany"}]},{"given":"Friedrich","family":"Kremer","sequence":"additional","affiliation":[{"name":"Peter Debye Institute for Soft Matter Physics Leipzig University  Linnestr. 5 04103 Leipzig 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