Effects of hydrogen bonds on two-photon absorption of Green fluorescent protein chromophore analogue

Abstract

Effects of hydrogen bonds on two-photon absorption (TPA) of a new donor-acceptor type green fluorescent protein chromophore analogue are investigated by employing a combined molecular dynamics and quantum chemistry method. The probable configurations of the chromophore in water are extracted from molecular dynamics simulation and the TP A properties of more than twenty hydrogen bond complexes are computed by quadratic response theory. Thereby, the structure and property relations are established. Three types of hydrogen bonds including O⋯H–O, N–H⋯O and N⋯H–O can be formed between the chromophore and water molecules. The O⋯H–O induces a little decrease of TPA cross section with a red-shifted wavelength. The N–H⋯O gives rise to a great enhancement of TP A at a longer wavelength, while the N⋯H–O decreases TP A significantly and makes the wavelength blue-shifted. The reasons for these effects are rationalized well by using a two-state model analysis. The related molecular orbitals are also plotted to visualize the charge transfer characters. In addition, the averaged TP A spectrum is obtained by calculating the probabilities of various hydrogen bond complexes. Our research could provide a good insight into the design of two-photon materials by making use of hydrogen bond networks.