Mixed Frequency/Time Domain Optical Analogues of Heteronuclear Multidimensional NMR

Ultrafast spectroscopy is dominated by time domain methods such as pump−probe and, more recently, 2D-IR spectroscopies. In this paper, we demonstrate that a mixed frequency/time domain ultrafast four wave mixing (FWM) approach not only provides similar capabilities, but it also provides optical analogues of multiple- and zero-quantum heteronuclear nuclear magnetic resonance (NMR). The method requires phase coherence between the excitation pulses only over the dephasing time of the coherences. It uses twelve coherence pathways that include four with populations, four with zero-quantum coherences, and four with double-quantum coherences. Each pathway provides different capabilities. The population pathways correspond to those of two-dimensional (2D) time domain spectroscopies, while the double- and zero-quantum coherence pathways access the coherent dynamics of coupled quantum states. The three spectral and two temporal dimensions enable the isolation and characterization of the spectral correlations between different vibrational and/or electronic states, coherence and population relaxation rates, and coupling strengths. Quantum-level interference between the direct and free-induction decay components gives a spectral resolution that exceeds that of the excitation pulses. Appropriate parameter choices allow isolation of individual coherence pathways. The mixed frequency/time domain approach allows one to access any set of quantum states with coherent multidimensional spectroscopy.