Electronic Substitution Effect on the Ground and Excited State Properties of Indole Chromophore: A Computational Study

Indole, being the main chromophore of amino acid tryptophan and several other biologically relevant molecules like serotonin, melatonin, has prompted considerable theoretical and experimental interest. The current work focuses on the investigation of substitution effect on the ground and excited electronic states of indole using computational quantum chemistry. Having three close-lying excited electronic states, the vibronic coupling effect becomes extremely important yet challenging for the photophysics and photochemistry of indole. Here, we have evaluated the performance of time-dependent density functional theory against available experimental and ab initio results from the literature. The electronic effects on the excited states of indole and indole derivatives e.g. tryptophan, serotonin and melatonin are reported. A bathochromic shift has been observed in the absorption spectrum for the state. The absorption wavelength increases in the order of indole tryptophan serotonin melatonin. While the contribution of the in-plane small adjacent groups increases the electron density of the indole ring, the out-of-plane long substituent groups have minor effect. The absorption spectra calculated including the vibronic coupling are in good agreement with experiments. These results can be used to estimate the error in photophysical observables of indole derivatives calculated considering indole as a prototypical system.

Automated summary

This study investigates the substitution effect on the ground and excited electronic states of indole using computational quantum chemistry. The performance of time-dependent density functional theory is evaluated against experimental and ab initio results. The results show that the substituents have a significant impact on the absorption spectrum and excited electronic states of indole, and the vibronic coupling effect is important for the photophysics and photochemistry of indole.