Two-Dimensional Electronic Spectroscopy Resolves Relative Excited-State Displacements.

Knowledge of relative displacements between potential energy surfaces (PES) is critical in spectroscopy and photochemistry. Information on displacements is encoded in vibrational coherences. Here we apply ultrafast two-dimensional electronic spectroscopy in a pump-probe half-broadband (HB2DES) geometry to probe the ground- and excited-state potential landscapes of cresyl violet. 2D coherence maps reveal that while the coherence amplitude of the dominant 585 cm -1 Raman-active mode is mainly localized in the ground-state bleach and stimulated emission regions, a 338 cm -1 mode is enhanced in excited-state absorption. Modeling these data with a three-level displaced harmonic oscillator model using the hierarchical equation of motion-phase matching approach (HEOM-PMA) shows that the S 1 ← S 0 PES displacement is greater along the 585 cm -1 coordinate than the 338 cm -1 coordinate, while S n ← S 1 displacements are similar along both coordinates. HB2DES is thus a powerful tool for exploiting nuclear wavepackets to extract quantitative multidimensional, vibrational coordinate information across multiple PESs.