Dual frequency 2D IR experiments were used to examine the intermode coupling, relaxation times and anharmonicities of two widely separated vibrational modes. In this report a weak intermode coupling and correlation between CH and CO modes of formamide and the relatively strong coupling between the NH mode of pyrrole and CO from dimethylacetamide (DMA) in benzene will be discussed. In both 2D IR and pump probe spectroscopy the population was initiated in the vibrational mode having the weaker transition dipole moment (CH and NH). The signal was collected in the frequency range of the strong CO mode. Off-diagonal anharmonicities of -0.85�0.20 cm-1 between CH and CO and +6�2 cm-1 between NH and CO were estimated from the photon echo and pump- probe experimental data. The dephasing dynamics of cross peaks have been measured on the sub picosecond time scale to characterize the correlation function and the coupling between modes. Finally, polarization controlled experiments were performed to find the angular alignment of coupled modes and the contributions of overall rotation to the dynamics. *This research was supported by grants from NIH (RR01348 and GM12592) and NSF CHE.