This article describes the new multidimensional spectroscopy technique triply resonant sum frequency spectroscopy, a four-wave mixing technique sharing advantages of both 2D-IR and resonance Raman experiments. In this technique, lasers with three independent frequencies interact coherently within a sample and generate an output frequency at their triple summation. The output intensity depends on coupled electronic and vibrational resonances in the sample. We use an organic dye as a model system to demonstrate fully resonant, fully coherent multidimensional spectroscopy using two independently tunable mid-infrared vibrational interactions and one visible electronic interaction. When the pulses are time ordered, the method has a single coherence pathway, eliminating interference between pathways. Fundamental vibrational transitions appear on one axis and overtones and combinations bands on the other, allowing anharmonicities of the modes to be determined easily and conveying molecular coupling information. The experiments demonstrate coupling between seven vibrational ring modes and an electronic state, the resolution of a Fermi resonance, detection of low concentrations, elimination of excitation pulse scattering and fluorescence, background suppression of solvent and co-solutes, and observation of coherence dephasing dynamics. The electronic resonance enhancements used in this methodology are similar to the enhancements responsible for resonance Raman spectroscopy and can be considered resonance 2D-IR spectroscopy.
This work demonstrates the use of triply resonant sum frequency (TRSF) spectroscopy as a "resonance IR" analogue to resonance Raman spectroscopy. TRSF is a four-wave-mixing process where three lasers with independent frequencies interact coherently with a sample to generate an output at their triple summation frequency. The first two lasers are in the infrared and result in two vibrational excitations, while the third laser is visible and induces a two-quantum anti-Stokes resonance Raman transition. The signal intensity grows when the laser frequencies are all in resonance with coupled vibrational and electronic states. The method therefore provides electronic enhancement of IR-active vibrational modes. These modes may be buried beneath solvent in the IR spectrum and also be Raman-inactive and therefore inaccessible by other techniques. The method is presented on the centrosymmetric complex copper phthalocyanine tetrasulfonate. In this study, the two vibrational frequencies were scanned across ring-breathing modes, while the visible frequency was left in resonance with the copper phthalocyanine tetrasulfonate Q band, resulting in a two-dimensional infrared plot that also reveals coupling between vibrational states. TRSF has the potential to be a very useful probe of structurally similar biological motifs such as hemes, as well as synthetic transition-metal complexes.
Triply resonant sum frequency (TRSF) spectroscopy is a fully coherent mixed vibrational−electronic spectroscopic technique that is ideally suited for probing the vibrational−electronic couplings that become important in driving reactions. We have used cyanocobalamin (CNCbl) and deuterated aquacobalamin (D 2 OCbl + ) as model systems for demonstrating the feasibility of using the selectivity of coherent multidimensional spectroscopy to resolve electronic states within the broad absorption spectra of transition metal complexes and identify the nature of the vibrational and electronic state couplings. We resolve three short and long axis vibrational modes in the vibrationally congested 1400−1750 cm −1 region that are individually coupled to different electronic states in the 18 000−21 000 cm −1 region but have minimal coupling to each other. Double resonance with the individual vibrational fundamentals and their overtones selectively enhances the corresponding electronic resonances and resolves features within the broad absorption spectrum. This work demonstrates the feasibility of identifying coupling between different pairs of vibrational states with different electronic states that together form the reaction coordinate surface of transition metal enzymes.
Triply resonant sum frequency (TRSF) and doubly vibrationally enhanced (DOVE) spectroscopies are examples of a recently developed family of coherent multidimensional spectroscopies (CMDS) that are analogous to multidimensional NMR and current analytical spectroscopies. CMDS methods are particularly promising for analytical applications because their inherent selectivity makes them applicable to complex samples. Like NMR, they are based on creating quantum mechanical superposition states that are fully coherent and lack intermediate quantum state populations that cause quenching or other relaxation effects. Instead of the nuclear spin states of NMR, their multidimensional spectral fingerprints result from creating quantum mechanical mixtures of vibrational and electronic states. Vibrational states provide spectral selectivity, and electronic states provide large signal enhancements. This paper presents the first electronically resonant DOVE spectra and demonstrates the capabilities for analytical chemistry applications by comparing electronically resonant TRSF and DOVE spectra with each other and with infrared absorption and resonance Raman spectra using a Styryl 9 M dye as a model system. The methods each use two infrared absorption transitions and a resonant Raman transition to create a coherent output beam, but they differ in how they access the vibrational and electronic states and the frequency of their output signal. Just as FTIR, UV-vis, Raman, and resonance Raman are complementary methods, TRSF and DOVE methods are complementary to coherent Raman methods such as coherent anti-Stokes Raman spectroscopy (CARS).
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