Energy funneling and macromolecular conformational dynamics: A 2D Raman correlation study of PEG melting

Ashok Zachariah Samuel, Siva Umapathy

Research output: Contribution to journalArticle

18 Citations (Scopus)


Cascading energy landscapes through funneling has been postulated as a mechanistic route for achieving the lowest energy configuration of a macromolecular system (such as proteins and polymers). In particular, understanding the molecular mechanism for the melting and crystallization of polymers is a challenging fundamental question. The structural modifications that lead to the melting of poly(ethylene glycol) (PEG) are investigated here. Specific Raman bands corresponding to different configurations of the PEG chain have been identified, and the molecular structural dynamics of PEG melting have been addressed using a combination of Raman spectroscopy, 2D Raman correlation and density functional theory (DFT) calculations. The melting dynamics of PEG have been unambiguously explained along the C-O bond rotation coordinate.

Original languageEnglish
Pages (from-to)330-336
Number of pages7
JournalPolymer Journal
Issue number6
Publication statusPublished - 2014
Externally publishedYes



  • Gauche effect
  • Melting dynamics
  • Polyethylene glycol
  • Raman spectroscopy
  • Two-dimensional correlation

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

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