[Frontiers in Bioscience 14, 4229-4241, January 1, 2009]

Rationalising the vibrational spectra of biomolecules using atomistic simulations

David M. Benoit

Nachwuchsgruppe Theorie - SFB 569, Albert-Einstein-Allee 11, University of Ulm, D-89081 Ulm, Germany

TABLE OF CONTENTS

1. Abstract
2. Introduction
2.1. Potential energy surfaces for biomolecules
3. Harmonic approximation for large molecular systems
3.1. Harmonic model
3.2. Scaling procedures
4. Beyond the harmonic approximation
4.1. Molecular-dynamics simulations
4.2. Perturbative approaches to anharmonicity
4.3. CC-VSCF towards solving the full-dimensional schrödinger equation
5. Applications
6. Perspectives
7. Acknowledgments
8. References

1. ABSTRACT

This review presents an account of the recent developments in the use of atomistic simulations to predict vibrational spectra of biomolecules. I give an overview of the concepts used in the various theoretical vibrational models and discuss their relative merits and weaknesses. The issue of anharmonicity in vibrational dynamics is examined in particular detail, owing to its crucial influence on simulations of vibrational spectra for flexible biosystems. The performance of each technique is illustrated by typical applications that show the latest work in this field on systems of biological interest, with a particular focus on the vibrational dynamics of the amide group in peptides.