Vibrational solvatochromism of nitrile infrared probes: Beyond the vibrational Stark dipole approach

Bartosz Błasiak, Andrew W. Ritchie, Lauren J. Webb, Minhaeng Cho

Research output: Contribution to journalArticlepeer-review

72 Citations (Scopus)


Systematic probing of local environments around biopolymers is important for understanding their functions. Therefore, there has been growing interest in in situ measurements of molecular granularity and heterogeneity through the systematic analysis of vibrational frequency shifts of carbonyl and nitrile infrared probes by vibrational Stark dipole theory. However, here we show that the nitrile vibrational frequency shift induced by its interaction with the surrounding molecules cannot be solely described by electric field-based theory because of the exchange-repulsion and dispersion interaction contributions. Considering a variety of molecular environments ranging from bulk solutions to protein environments, we explore the distinct scenarios of solute-environment contacts and their traces in vibrational frequency shifts. We believe that the present work could provide a set of clues that could be potentially used to design a rigorous theoretical model linking vibrational solvatochromism and molecular topology in complex heterogeneous environments.

Original languageEnglish
Pages (from-to)18094-18111
Number of pages18
JournalPhysical Chemistry Chemical Physics
Issue number27
Publication statusPublished - 2016

Bibliographical note

Funding Information:
This work was supported by IBS-R023-D1 and the Welch Foundation (Grant No. F-1722). The authors gratefully acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin and the Wrocław Centre for Networking and Supercomputing (WCSS) at Wrocław University of Technology in Poland for providing high-performance computing resources that have contributed to the results within this paper.

Publisher Copyright:
© the Owner Societies 2016.

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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