Polarizable Embedding Combined with the Algebraic Diagrammatic Construction: Tackling Excited States in Biomolecular Systems

• DOI: 10.1021/acs.jctc.8b00576
• Publication Date: 2018-08-07T22:37:31Z
• Authors: Maximilian Scheurer; Michael F. Herbst; Peter Reinholdt; Jógvan Magnus Hau...; Andreas Dreuw; Jacob Kongsted
• Keywords: Models, Molecular; Aniline Compounds; Flavins/chemistry; Molecular; Water; Electrons; 01 natural sciences; Models; Water/chemistry; Flavins; 0103 physical sciences; Aniline Compounds/chemistry; Quantum Theory

We present a variant of the algebraic diagrammatic construction (ADC) scheme by combining ADC with the polarizable embedding (PE) model. The presented PE-ADC method is implemented through second and third order and is designed with the aim of performing accurate calculations of excited states in large molecular systems. Accuracy and large-scale applicability are demonstrated with three case studies, and we further analyze the importance of both state-specific and linear-response-type corrections to the excitation energies in the presence of the polarizable environment. We demonstrate how our combined method can be readily applied to study photoinduced biochemical processes as we model the charge-transfer (CT) excitation which is key to the photoprotection mechanism in the dodecin protein with PE-ADC(2). Through direct access to state-of-the-art excited state analysis, we find that the polarizable environment plays a decisive role by significantly increasing the CT character of the electronic excitation in dodecin. PE-ADC is thus suited to decipher photoinduced processes in complex, biomolecular systems at high precision and at reasonable computational cost.