This is the first in a two-paper series that investigates the influence of intramolecular vibrational modes on nonlinear, time-domain, electronically resonant signals. Both Transient Grating (TG) and Three Pulse Photon Echo Peak Shift (3PEPS) signals were collected from several probe molecules: Nile Blue, N,N-bis-dimethylphenyl-2,4,6,8-perylenetetracarbonyl diamide, and Rhodamine 6G dissolved in different solvents: benzene, dimethylsulfoxide, and acetonitrile. The effects of excitation of different vibronic transitions on the electronically resonant signals were identified by comparing signals collected with laser pulses at different excitation wavelengths. In the 3PEPS profiles, we find that excitation on the blue edge of the absorption spectrum causes a decreased initial peak shift values and more rapid initial decays, whilst in the TG signals, the magnitude of the “coherent spike” is strongly wavelength dependent. Additional thermally activated vibronic effects were studied via temperature dependent 3PEPS profiles. Our results reveal the sensitivity of the nonlinear signals to the excitation wavelengths and to the distinct vibronic structure of the different chromophores studied. Pronounced modulations in both the 3PEPS and TG signals originating from coherently excited vibrational modes were directly observed. Additional oscillations were observed that are attributed to difference frequencies and higher harmonics of the fundamental modes. In paper II we demonstrate that detailed account of the vibronic nature of the chromophore is required to describe the wavelength dependent signals.

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