Two-dimensional Fano lineshapes in ultrafast vibrational spectroscopy of thin molecular layers on plasmonic arrays

Two-dimensional femtosecond infrared (2DIR) spectroscopy routinely provides insights into molecular structure and ultrafast dynamics in 1–100 μm thick bulk samples. Confinement of molecules to surfaces, gaps, crevices, and other topographic features, frequently encountered on the nanometer length scale, significantly alters their structure and dynamics, affecting physical and chemical properties. Amplification of 2DIR signals by the plasmon-enhanced fields around metal nanostructures can permit structural and dynamics measurements of the confined molecules. Fano resonances, induced by the interaction between laser pulses, plasmon, and vibrational modes significantly distort 2D lineshapes. For different detuning from plasmon resonance, the interference between multiple signal components leads to different line shape asymmetry, which we demonstrate on a set of linear absorption, transient absorption, and 2DIR spectra. An intuitive model used to describe experimental data points to the interference’s origin. Our results will facilitate the application of surface-enhanced 2DIR spectroscopy for studies of molecular structure and dynamics in a nanoconfined environment.
Authors: Andrey Gandman, Robert Mackin, Bar Cohn, Igor V Rubtsov, Lev Chuntonov

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A Spin-Boson Screening approach for unraveling dominant vibrational energy transfer pathways in molecular materials

Vibrational energy transfer driven by anharmonicity is the major mechanism of energy dissipation in polyatomic molecules and in molecules embedded in condensed phase environment. Energy transfer pathways are sensitive to the particular intra-molecular structure as well as to specific interactions between the molecule and its environment, and their identification is a challenging many-body problem. This work introduces a theoretical approach which enables to identify the dominant pathways for specified initial excitations, by screening the different possible relaxation channels. For each channel, the many-body Hamiltonian is mapped onto a respective all-vibrational Spin-Boson Hamiltonian, expressed in terms of the harmonic frequencies and the anharmonic coupling parameters obtained from the electronic structure of the molecule in its environment. A focus is given on the formulation of the relaxation rates when different limits of perturbation theory apply. In these cases the proposed Spin-Boson Screening approach becomes especially powerful.
Authors: Lev Chuntonov, Uri Peskin

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