Excited States and Dynamics of Functional Re(I) Complexes Embedded in Metalloproteins-Development of New Theoretical Methods for the Simulation and Control of Excited-State Properties and Reactivity in Biological Environments – DeNeTheor

DeNeTheor requires the combined expertise of (i) methods able to accurately calculate excited states of complex chromophores including transition metal complexes, (ii) reaction dynamics techniques (such as QD and AIMD), and (iii) approaches to evaluate the impact of a biological environment, such as QM/MM methods alone or coupled with AIMD.

Interface bewteen SHARC, a program for non-adiabatic molecular dynamics including spin-orbit-coupling, and time-dependent density fucntional theory -
Exploitation of the QM:MM methods within SHARC protocole in order to take into account complex environment effects (water, DNA, protein...)

To solve the mechanism of accelerated electron-transfer in modified copper proteins linked to transition metal chromophores at the multiscale level in time and in space.

Publications - scientific meetings - softwares - new knowledge

DeNeTheor aims at modeling and simulating light-responsive molecular systems in complex bio-environments, namely proteins and macromolecular matrices. Excited states and photoinduced dynamics of a series of Re (I) complexes embedded in metallolabeled mutants of a blue copper protein will be studied. Depending of the surrounding ligands and of the environment, specific functions, such as electron transfer triggering, luminescent probe or isomerization can be achieved opening the route to a number of important applications in material sciences and molecular biology. Novel theoretical tools and multi-scale computational strategies based on quantum mechanics (QM), quantum dynamics (QD), molecular mechanics (MM) and molecular dynamics (MD) will de developed for handling these systems. Spin-vibronic couplings will be considered in the modeling of the dynamics of the isolated chromophores and in the presence of environments of increasing complexity.
This ambitious goal will be achieved through the combination of three groups with complementary expertises: (1) the calculation of electronically excited states for transition metal complexes with accurate multi-reference quantum chemical methods (Strasbourg), (2) the simulation of dynamical processes with nuclear wavepackets (Strasbourg) and with ab initio MD (AIMD) methods (Vienna) and (3) the description of complex biological environments with hybrid QM/MM techniques (Nancy). The expertises of the groups of Strasbourg, Vienna, and Nancy will be combined to develop novel tools able to describe electronic excited states properties and reactivity with enough accuracy. Their time evolution will be properly described, as well as their interaction with complex surroundings that may tune or modify their properties and dynamics.
The planned consortium will enable collaborative research as well as active exchange of knowhow and competences that will lead to the following key achievements:
i) Development of new computational schemes suitable to consider biological environments combining QM/MM and AIMD methods, to describe dynamics both in the ground and excited states;
ii) Exploitation of highly accurate QM methods, taking into account spin-orbit and vibronic couplings within the framework of QM/MM approaches;
iii) Production and dissemination of original computational chemistry protocols to model photonic properties and light-induced processes;
iv) Exploration of the interplay between transition metal complexes and biological structures featuring several functions under light control.


DeNeTheor will greatly enhance the cooperation and transfer of knowledge between the three participating teams and, also very importantly, will promote the participation and qualification of young researchers, involved in each of the teams. The planned objectives cannot be achieved by a single team. Instead, this consortium is designed to gather complementary know-how in different competences and will allow for synergetic advances, especially in the field of method development.