Vibrationally resolved two-photon electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy with two-photon excitation.

Following up on our previous work on vibrationally resolved electronic absorption spectra including the effect of vibrational pre-excitation [von Cosel et al., J. Chem. Phys. 147, 164116 (2017)], we present a combined theoretical and experimental study of two-photon-induced vibronic transitions in polyatomic molecules that are probed in the VIbrationally Promoted Electronic Resonance experiment using two-photon excitation (2P-VIPER). In order to compute vibronic spectra, we employ time-independent and time-dependent methods based on the evaluation of Franck-Condon overlap integrals and Fourier transformations of time-domain correlation functions, respectively. The time-independent approach uses a generalized version of the FCclasses method, while the time-dependent approach relies on the analytical evaluation of Gaussian moments within the harmonic approximation, including Duschinsky rotation effects. For the Coumarin 6 dye, two-dimensional 2P-VIPER experiments involving excitation to the lowest-lying singlet excited state (S1) are presented and compared with corresponding one-photon VIPER spectra. In both cases, coumarin ring modes and a CO stretch mode show VIPER activity, albeit with different relative intensities. Selective pre-excitation of these modes leads to a pronounced redshift of the low-frequency edge of the electronic absorption spectrum, which is a prerequisite for the VIPER experiment. Theoretical analysis underscores the role of interference between Franck-Condon and Herzberg-Teller effects in the two-photon experiment, which is at the root of the observed intensity distribution.

A Triplet Label Extends Two-Dimensional Infrared Spectroscopy from Pico- to Microseconds.

In conventional two-dimensional infrared (2D-IR) spectroscopy, the inherently short vibrational lifetimes limit the time window to observe molecular dynamics typically to tens of picoseconds. The rather complex dynamics of organized molecular systems (e.g., glass formers, polymers, membranes, proteins), however, span a wide range of timescales from femto- to microseconds and beyond. Vibrationally Promoted Electronic Resonance (VIPER) 2D-IR negates the limitations of 2D-IR spectroscopy, for its signal decays with the electronic lifetime. Here, we present 2-Isopropylthioxanthone as the first VIPER 2D-IR probe to exploit intersystem crossing, thereby covering even the microsecond timescale. We achieved the required signal-to-noise ratio and resolution by introducing the Fourier-transform approach to the VIPER 2D-IR pulse sequence. Now, we are in a position to monitor dynamics via spectral diffusion several orders of magnitude beyond the vibrational lifetime of 2D-IR labels.