James D. Gaynor

Fourier transform two-dimensional electronic-vibrational spectroscopy using an octave-spanning mid-IR probe

The development of coherent Fourier transform two-dimensional electronic-vibrational (2D EV) spectroscopy with acousto-optic pulse-shaper-generated near-UV pump pulses and an octave-spanning broadband mid-IR probe pulse is detailed. A 2D EV spectrum of a silicon wafer demonstrates the full experimental capability of this experiment, and a 2D EV spectrum of dissolved hexacyanoferrate establishes the viability of our 2D EV experiment for studying condensed phase molecular ensembles.

Compression of tunable broadband mid-IR pulses with a deformable mirror pulse shaper

To improve the utility of ultrafast infrared spectroscopy experiments, we have developed and actively compressed a tunable broadband mid-IR (BBIR) source. The octave-spanning BBIR source is generated by a filamentation process of 800 and 400 nm pulses in a pressurized gas cell. To correct the higher-order dispersion effects in BBIR pulses, we have introduced a deformable mirror grating compressor, which uses an iterative genetic algorithm with optical feedback. Compression yields nearly transform-limited BBIR pulses of 21 fs, or ∼1.4 optical cycles at the center frequency, as measured by cross-correlation frequency resolved optical gating.

Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies

Two-Dimensional Electronic-Vibrational (2D EV) spectroscopy and Two-Dimensional Vibrational-Electronic (2D VE) spectroscopy are new coherent four-wave mixing spectroscopies that utilize both electronically resonant and vibrationally resonant field-matter interactions to elucidate couplings between electronic and vibrational degrees of freedom. A system Hamiltonian is developed here to lay a foundation for interpreting the 2D EV and 2D VE signals that arise from a vibronically coupled molecular system in the condensed phase. A molecular system consisting of one anharmonic vibration and two electronic states is modeled. Equilibrium displacement of the vibrational coordinate and vibrational frequency shifts upon excitation to the first electronic excited state are included in our Hamiltonian through linear and quadratic vibronic coupling terms. We explicitly consider the nuclear dependence of the electronic transition dipole moment and demonstrate that these spectroscopies are sensitive to non-Condon effects. A series of simulations of 2D EV and 2D VE spectra obtained by varying parameters of the system, system-bath, and interaction Hamiltonians demonstrate that one of the following conditions must be met to observe signals: (1) non-zero linear and/or quadratic vibronic coupling in the electronic excited state, (2) vibrational-coordinate dependence of the electronic transition dipole moment, or (3) electronic-state-dependent vibrational dephasing dynamics. We explore how these vibronic interactions are manifested in the positions, amplitudes, and line shapes of the peaks in 2D EV and 2D VE spectroscopies.

Mapping Vibronic Couplings in a Solar Cell Dye with Polarization-Selective Two-Dimensional Electronic-Vibrational Spectroscopy

This study uses polarization-selective two-dimensional electronic-vibrational (2D EV) spectroscopy to map intramolecular charge transfer in the well-known solar cell dye, [Ru(dcbpy)2(NCS)2]4- (N34-), dissolved in water. A static snapshot of the vibronic couplings present in aqueous N34- is reported. At least three different initially excited singlet metal-to-ligand charge-transfer (MLCT) states are observed to be coupled to vibrational modes probed in the lowest energy triplet MLCT state, emphasizing the role of vibronic coupling in intersystem crossing. Angles between electronic and vibrational transition dipole moments are extracted from spectrally isolated 2D EV peaks and compared with calculations to develop a microscopic description for how vibrations participate with 1MLCT states in charge transfer and intersystem crossing. These results suggest that 1MLCT states with significant electron density in the electron-donating plane formed by the Ru-(NCS)2 will participate strongly in charge transfer through these vibronically coupled degrees of freedom.