Electron Attachment to DNA and RNA Nucleobases: An EOMCC Investigation

TL;DR

This study uses advanced EOMCC computational methods to accurately determine electron affinities of DNA and RNA nucleobases, clarifying their stability and nature, and providing reliable benchmark data.

Contribution

It provides the first comprehensive EOMCC-based benchmark of electron affinities for DNA and RNA nucleobases, resolving previous discrepancies and confirming the resonance nature of their electron-attached states.

Findings

First electron attached states are mostly resonance states with negative affinities.

Valence-bound states in uracil and thymine undergo structural changes upon electron attachment.

Dipole-bound states in cytosine, adenine, and guanine remain structurally unaffected.

Abstract

We report a benchmark theoretical investigation of both adiabatic and vertical electron affinities of five DNA and RNA nucleobases: adenine, guanine, cytosine, thymine and uracil using state-of-the-art equation of motion coupled cluster (EOMCC) method. We have calculated the vertical electron affinity values of first five electron attached states of the DNA and RNA nucleobases and only the first electron attached state is found to be energetically accessible in gas phase. An analysis of the natural orbitals shows that the first electron attached states of uracil and thymine are valence-bound type and undergo significant structural changes on attachment of excess electron, which is reflected in the deviation of the adiabatic electron affinity from the vertical one. On the other hand, the first electron attached state of cytosine, adenine and guanine are dipole-bound type and their structure remain unaffected on attachment of an extra electron, which results in small deviation of adiabatic electron affinity from that of the vertical one. Vertical and adiabatic electron affinity values of all the DNA and RNA nucleobases are negative implying that the first electron attached state are not stable, but rather resonance states. Previously, reported theoretical studies had shown scattered results for electron affinities of DNA and RNA bases, with large deviations from experimental values. Our EOMCC computed values are in very good agreement with experimental values and can be used as a reliable benchmark for calibrating new theoretical methods.