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Structure and dynamics of trimethylacetonitrile at the silica/vapor, silica/liquid, and liquid/vapor interfaces

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Published copy (DOI)

Author(s)

  • Feng Ding
  • Christopher A. Rivera
  • Qin Zhong
  • Katherine Manfred
  • Xiaoxiao He
  • Michael R. Brindza
  • Robert A. Walker
  • John T. Fourkas

Department/unit(s)

Publication details

JournalJournal of Physical Chemistry C
DatePublished - 29 Mar 2012
Issue number12
Volume116
Number of pages10
Pages (from-to)7000-7009
Original languageEnglish

Abstract

Optical spectroscopy has been used to probe the interfacial organization and dynamics of trimethylacetonitrile (TMACN). Molecular orientation at the silica/liquid, silica/vapor and liquid/vapor interfaces of TMACN has been studied using vibrational sum-frequency generation (VSFG) spectroscopy. These studies reveal that TMACN exhibits appreciable organization at each of these interfaces, despite the bulky nature of its tert-butyl group. VSFG spectra measured from the silica/liquid interface suggest that TMACN does not form the sort of well-organized bilayer that has been observed previously for acetonitrile and propionitrile. Optical Kerr effect studies of TMACN confined in porous silica glasses demonstrate that this liquid forms a dynamically inhibited surface layer that is roughly one molecule thick, which is consistent with the organizational model suggested by the VSFG data.

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