Quantum chemical benchmark studies of the electronic properties of the green fluorescent protein chromophore: I. Electronically excited and ionized states of the anionic chromophore in the gas phase

E. Epifanovsky, I. Polyakov, B. Grigorenko, A.V. Nemukhin, and A.I. Krylov
J. Chem. Theor. Comput. 5, 1895 – 1906 (2009)

We present the results of quantum chemical calculations of the electronic properties of the anionic form of the green fluorescent protein (GFP) chromophore in the gas phase. The vertical detachment energy of the chromophore is found to be 2.4-2.5 eV, which is below the strongly absorbing pi-pi* state at 2.6 eV. The vertical excitation of lowest triplet state is around 1.9 eV, which is below the photodetachment continuum. Thus, the lowest bright singlet state is a resonance state embedded in photodetachment continuum, whereas the lowest triplet state is a regular bound state. Based on our estimation of the vertical detachment energy, we attribute a minor feature in the action spectrum as due to the photodetachment transition. The benchmark results for the bright pi-pi* state demonstrated that scaled opposite-spin CIS(D) method yields vertical excitation within 0.1 eV (20 nm) from the experimental maximum at 2.59 eV (479 nm). We also report estimations of the vertical excitation energy obtained with the equation-of-motion coupled-cluster with singles and doubles method (EOM-CCSD), a multireference perturbation theory corrected approach MRMP2, as well as time-dependent density functional theory (TD-DFT) with range-separated functionals. Expanding the basis set with diffuse functions lowers the pi-pi* vertical excitation energy by 0.1 eV at the same time revealing a continuum of ``ionized'' states, which embeds the bright pi-pi* transition.

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