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Vibrational Exciton Models for Biomolecules from Quantum Chemistry

Subject Area Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
Biophysics
Term from 2015 to 2022
Project identifier Deutsche Forschungsgemeinschaft (DFG) - Project number 277079088
 
Final Report Year 2024

Final Report Abstract

Vibrational spectroscopy can provide insights into fast processes occurring during protein folding and in disordered or unfolded proteins. In this project, we have developed efficient computational methods for reliably predicting vibrational spectra of biomolecular systems, in particular for two-dimensional infrared (2D-IR) and vibrational Raman optical activity (ROA) spectroscopy of conformationally flexible polypeptides and proteins. The key idea of all these developments is the use of localized vibrational modes as starting point. In this project, we have (a) further developed efficient L-VSCF/L-VCI methods for the calculation of anharmonic vibrational spectra, (b) explored the use of localized modes for constructing efficient vibrational exciton models from quantum-chemical calculations, and (c) pursued the calculation of ROA and 2D-IR spectra based on these novel methods. Specifically, we have (a) performed the first L-VSCF/L-VCI calculation of the anharmonic ROA spectrum of a system as large as (Ala)20 , which revealed that anharmonicities do not alter ROA band shapes significantly, (b) performed the first quantum-chemical calculations of 2D-IR spectra of polypeptides, and made the first predictions for 2D-IR spectra in the extended amide III region. The developments made in this project open the door to large-scale computational studies of advanced vibrational spectroscopy for realistic models of biomolecular systems.

Link to the final report

https://doi.org/10.24355/dbbs.084-202501161006-0

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