Micro-Solvated DMABN: Excited State Quantum Dynamics and Dual Fluorescence Spectra

In this work, we report a complete analysis by theoretical and spectroscopic methods of the short-time behaviour of 4-(dimethylamino)benzonitrile (DMABN) in the gas phase as well as in cyclohexane, tetrahydrofuran, acetonitrile, and water solution, after excitation to the La state. The spectroscopic properties of DMABN were investigated experimentally using UV absorption and fluorescence emission spectroscopy. The computational study was developed at different electronic structure levels and using the Polarisable Continuum Model (PCM) and explicit solvent molecules to reproduce the solvent environment. Additionally, excited state quantum dynamics simulations in the diabatic picture using the direct dynamics variational multiconfigurational Gaussian (DD-vMCG) method were performed, the largest quantum dynamics on-the-fly simulations performed with this method until now. The comparison with fully converged multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) dynamics on parametrised linear vibronic coupling (LVC) potentials show very similar population decays and evolution of the nuclear wavepacket. The ring C=C stretching and three methyl tilting modes are identified as the responsible motions for the internal conversion from the La to the Lb states. No major differences are observed in the ultrafast initial decay in different solvents, but we show that this effect depends strongly on the level of electronic structure used.

Automated summary

This study presents a complete analysis of the short-time behavior of 4-(dimethylamino)benzonitrile (DMABN) in different environments after excitation to the La state, with a focus on the ring C=C stretching and three methyl tilting modes as responsible motions for the internal conversion. The comparison with ML-MCTDH dynamics on LVC potentials shows similar population decays and nuclear wavepacket evolution, highlighting the importance of the electronic structure level used in influencing ultrafast initial decay in different solvents.