Carboxylate Anchors Act as Exciton Reporters in 1.3 nm Indium Phosphide Nanoclusters

Joel D. Leger, Max R. Friedfeld, Ryan A. Beck, James D. Gaynor, Alessio Petrone, Xiaosong Li, Brandi M. Cossairt, Munira Khalil*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

Developing interfacial probes of ligand-nanocluster interactions is crucial for understanding and tailoring the optoelectronic properties of these emerging nanomaterials. Using transient IR spectroscopy, we demonstrate that ligand vibrational modes of oleate-capped 1.3 nm InP nanoclusters report on the photogenerated exciton. The exciton induces an intensity change in the asymmetric carboxylate stretching mode by 57% while generating no appreciable shift in frequency. Thus, the observed difference signal is attributed to an exciton-induced change in the dipole magnitude of the asymmetric carboxylate stretching mode. Additionally, the transient IR data reveal that the infrared dipole change is dependent on the geometry of the ligand bound to the nanocluster. The experimental results are interpreted using TDDFT calculations, which identify how the spatial dependence of an exciton-induced electron density shift affects the vibrational motion of the carboxylate anchors. More broadly, this work demonstrates transient IR spectroscopy as a useful method for characterizing ligand-nanocluster coupling interactions.

Original languageEnglish (US)
Pages (from-to)1833-1839
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume10
Issue number8
DOIs
StatePublished - Apr 18 2019

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry

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