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Updated: Sep 23, 2025

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Ultrafast Vibrational Response of Activated C-D Bonds in a Chloroform-Platinum(II) Complex
Jia Zhang1, Achintya Kundu1, Thomas Elsaesser1
1Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie, 12489 Berlin, Germany.
Abstract:
The vibrational response of the activated C-D bond in the chloroform complex [Pt(C6H5)2(btz-N,N')·CDCl3, where btz = 2,2'-bi-5,6-dihydro-4H-1,3-thiazine] is studied by linear and nonlinear two-dimensional infrared (2D-IR) spectroscopy. The change of the C-D stretching vibration of metal-coordinated CDCl3 relative to the free solvent molecule serves as a measure of the non-classical Pt···D-C interaction strength. The stretching absorption band of the activated C-D bond displays a red shift of 119 cm-1 relative to uncoordinated CDCl3, a strong broadening, and an 8-fold enhancement of spectrally integrated absorption. The infrared (IR) absorption and 2D-IR line shapes are governed by spectral diffusion on 200 fs and 2 ps time scales, induced by the fluctuating solvent CDCl3. The enhanced vibrational absorption and coupling to solvent forces are assigned to the enhanced electric polarizability of the activated C-D bond. Density functional theory calculations show a significant increase of C-D bond polarizability of CDCl3 upon coordination to the 16 valence electron Pt(II) complex.
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