Ab initio based building block model of amide I vibrations in peptides

Abstract

Various methods to parameterize an exciton model of amide I vibrations are suggested and analyzed. In the spirit of a systematic fragmentation scheme, small model peptides are employed as building-blocks to construct the vibrations of a polypeptide. As an example, extensive density functional theory (DFT) calculations at the B3LYP/6-31+G(d) theoretical level of glycine tripeptide are presented, which serve as reference data for testing various approximate schemes. The combination of a DFT description of next-neighbor interactions via dipeptide building blocks combined with an electrostatic model to account for the long-range interactions appears as a promising approach to achieve spectroscopic accuracy at low computational cost.