Vibrational heavy atom effect controls relaxation and spectral diffusion in triphenyl hydride complexes

Cynthia G. Pyles, Courtney M. Olson, Aaron M. Massari

Research output: Contribution to journalArticlepeer-review

4 Scopus citations


A series of three triphenyl hydride compounds was investigated in a range of solvents by Fourier transform infrared (FTIR), IR pump-probe, and two-dimensional IR (2D-IR) spectroscopies. The mass of the central atom of the three compounds was varied systematically down the group 14 elements of silicon, germanium, and tin. FTIR studies provided evidence that the solvent perturbs the three hydride modes in a similar manner, as indicated by identical solvatochromic and broadening trends. IR pump-probe measurements showed that the vibrational lifetime of the hydride stretch increased when the mass of the central atom increased. Density functional theory calculations asserted that the vibrational modes of the three compounds are nearly identical except for the hydride stretching and wagging modes. Interestingly, frequency-frequency correlation functions obtained from 2D-IR spectra indicated that an increasingly large central atom produces small, but measurable changes in the dynamics of the solvation shell surrounding each compound.

Original languageEnglish (US)
Pages (from-to)98-103
Number of pages6
JournalChemical Physics
StatePublished - Aug 17 2018

Bibliographical note

Funding Information:
The authors gratefully acknowledge funding from the National Science Foundation under CHE-1464416 . The authors thank Prof. Joseph Topczewski (U of MN) for synthesis and characterization of TriPS- d 1 .

Publisher Copyright:
© 2018 Elsevier B.V.


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