# Excitation of Nucleobases from a Computational Perspective II: Dynamics

## TL;DR

This paper reviews computational methods for studying the relaxation dynamics of isolated DNA/RNA nucleobases after photoexcitation, comparing different approaches and their results with experimental data.

## Contribution

It provides a comprehensive comparison of electronic structure and dynamics methods used in simulating nucleobase relaxation processes and discusses mechanistic differences among nucleobases.

## Key findings

- Different computational methods yield varying relaxation pathways.
- The Tully surface hopping with on-the-fly CASSCF is most commonly used.
- Mechanistic similarities and differences between purines and pyrimidines are elucidated.

## Abstract

This Chapter is devoted to unravel the relaxation processes taking place after photoexcitation of isolated DNA/RNA nucleobases in gas phase from a time-dependent perspective. To this aim, several methods are at hand, ranging from full quantum dynamics to various flavours of semiclassical or ab initio molecular dynamics, each with its advantages and its limitations. As this contribution shows, the most common approach employed up-to-date to learn about the deactivation of nucleobases in gas phase is a combination of the Tully surface hopping algorithm with on-the-fly CASSCF calculations. Different methods or, even more dramatically, different electronic structure methods can provide different dynamics. A comprehensive review of the different mechanisms suggested for each nucleobase is provided and compared to available experimental time scales. The results are discussed in a general context involving the effects of the different applied electronic structure and dynamics methods. Mechanistic similarities and differences between the two groups of nucleobases---the purine derivatives (adenine and guanine) and the pyrimidine derivatives (thymine, uracil, and cytosine)---are elucidated. Finally, a perspective on the future of dynamics simulations in the context of nucleobase relaxation is given.