Development of interface-/surface-specific two-dimensional electronic spectroscopy

Structures, kinetics, and chemical reactivities at interfaces and surfaces are key to understanding many of the fundamental scientific problems related to chemical, material, biological, and physical systems. These steady-state and dynamical properties at interfaces and surfaces require even-order techniques with time-resolution and spectral-resolution. Here, we develop fourth-order interface-/surface-specific two-dimensional electronic spectroscopy, including both two-dimensional electronic sum frequency generation (2D-ESFG) spectroscopy and two-dimensional electronic second harmonic generation (2D-ESHG) spectroscopy, for structural and dynamics studies of interfaces and surfaces. The 2D-ESFG and 2D-ESHG techniques were based on a unique laser source of broadband short-wave IR from 1200 nm to 2200 nm from a home-built optical parametric amplifier. With the broadband short-wave IR source, surface spectra cover most of the visible light region from 480 nm to 760 nm. A translating wedge-based identical pulses encoding system (TWINs) was introduced to generate a phase-locked pulse pair for coherent excitation in the 2D-ESFG and 2D-ESHG. As an example, we demonstrated surface dark states and their interactions of the surface states at p-type GaAs (001) surfaces with the 2D-ESFG and 2D-ESHG techniques. These newly developed time-resolved and interface-/surface-specific 2D spectroscopies would bring new information for structure and dynamics at interfaces and surfaces in the fields of the environment, materials, catalysis, and biology.