Electronic State-Resolved Multimode-Coupled Vibrational Wavepackets in Oxazine 720 by Two-Dimensional Electronic Spectroscopy.

Abstract

The difference between the excited- and ground-state vibrational wavepackets remains to be fully explored when multiple vibrational modes are coherently excited simultaneously by femtosecond pulses. In this work, we present a series of one- and two-dimensional electronic spectroscopy for studying multimode wavepackets of oxazine 720 in solution. Fourier transform (FT) maps combined with time-frequency transform (TFT) are employed to unambiguously distinguish the origin of low-frequency vibrational wavepackets, that is, an excited-state vibrational wavepacket of 586 cm-1 with a dephasing time of 0.7 ps and a ground-state vibrational wavepacket of 595 cm-1 with a dephasing time of 1.3-1.7 ps. We also found the additional low-frequency vibrational wavepackets resulting from the coupling of the 595 cm-1 mode to a series of high-frequency modes centered at 1150 cm-1 via electronic transitions. The combined use of FT maps and TFT analysis allows us to reveal the potential vibrational coupling of wavepackets and offers the possibility of disentangling the coupling between the electronic and vibrational degrees of freedom in condensed-phase systems.