Ultrafast intramolecular vibrational energy transfer in carbon nitride hydrocolloid examined by femtosecond two-dimensional infrared spectroscopy.

Abstract

In this work, ultrafast vibrational and structural processes in a graphitic carbon nitride hydrocolloid system were studied using a combination of linear infrared and nonlinear two-dimensional infrared (2D IR) spectroscopies. The experimentally observed three IR line shapes in the C=N stretching vibration frequency region were analyzed and attributed to the rigid and conjugated molecular frame of the prepared g-CN molecular species, which is believed to be a dimeric tris-s-triazine, as well as attributed to insignificant solvent influence on the delocalized C=N vibrations. Vibrational transition density cubes were also computed for the proposed g-CN dimer, confirming the heterocyclic C=N stretching nature of the three IR absorption peaks. Intramolecular vibrational energy transfer dynamics and spectral diffusion of the g-CN system were characterized by examining a series of time-dependent 2D IR spectra. A picosecond intramolecular vibrational energy redistribution process was found to occur among these delocalized C=N stretching modes, acting as an efficient vibrational energy transfer channel. This work reasonably connects the experimentally observed IR signature to a specific g-CN structure and also provides the first report on the ultrafast intramolecular processes of such carbon nitride systems. The obtained results are fundamentally important for understanding the molecular mechanisms of such carbon-nitride based functional materials.