Many-Body Perturbation Theory Extended to the Quantum Mechanics/Molecular Mechanics Approach: Application to Indole in Water Solution

• Published in: Journal of chemical theory and computation Vol. 5; no. 7; pp. 1822 - 1828
• Main Authors: Conte, Adriano Mosca, Ippoliti, Emiliano, Del Sole, Rodolfo, Carloni, Paolo, Pulci, Olivia
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 14.07.2009
• Subjects: Spectroscopy and Excited States
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/ct800528e

Optical properties of aromatic chromophores are used to probe complex biological processes, yet how the environment tunes their optical properties is far from being fully understood. Here we present a method to calculate such properties on large-scale systems, like biologically relevant molecules in aqueous solution. Our approach is based on many-body perturbation theory combined with a quantum mechanics/molecular mechanics (QM/MM) approach. We include quasiparticle and excitonic effects for the calculation of optical absorption spectra in a QM/MM scheme. We apply this scheme, together with the well-established TDDFT approach, to indole in water solution. Our calculations show that the solvent induces a red shift in the main spectral peak of indole, in quantitative agreement with the experiments, and they point to the relevance of both the electrostatic and geometrical origin of the shift.