Electronic states of neutral and ionized tetrahydrofuran studied by VUV spectroscopy and ab initio calculations

A Giuliani,M.-J Hubin-Franskin,P Limão-Vieira,B P Marinkovic,D Duflot,S V Hoffmann,A R Milosavljevic,J Delwiche,N Mason

doi:10.1140/epjd/e2008-00154-7

Abstract

The electronic spectroscopy of isolated tetrahydrofuran (THF) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 5.8–10.6 eV with absolute cross-section measurements derived. In addition, an electron energy loss spectrum was recorded at 100 eV and 10° over the 5–11.4 eV range. The He(I) photoelectron spectrum was also collected to quantify ionisation energies in the 9–16.1 eV spectral region. These experiments are supported by the first high-level ab initio calculations performed on the excited states of the neutral molecule and on the ground state of the positive ion. The excellent agreement between the theoretical results and the measurements allows us to solve several discrepancies concerning the electronic state spectroscopy of THF. The present work reconsiders the question of the lowest energy conformers of the molecule and its population distribution at room temperature.

Highlights

Tetrahydrofuran (THF) is a five membered heterocyclic ring that is often used as a chemical and molecular model for theribose ring in nucleic acids
It is worth noting that, as previously mentioned by Cadioli et al [22], results from X-rays [44] and neutron diffraction [45] experiments are consistent with the C2 geometry, as seen from the values of dihedral angle involving the ring at supplementary information table 1
Rayón and Sordo [24] have pointed out that the potential energy surface (PES) is nearly flat, which makes the characterisation of geometries as the extrema along the pseudo-rotational coordinate a challenging task

Summary

Introduction

Tetrahydrofuran (THF) is a five membered heterocyclic ring that is often used as a chemical and molecular model for the (deoxy)ribose ring in nucleic acids. In particular ionising radiation liberates large numbers of low energy secondary electrons [1]. These secondary electrons, despite having energies below the ionization threshold, can induce significant amounts of both single and double strand breaks within the cellular DNA [2] in turn providing the origin of mutations or inducing cellular death [3]. THF provides a good analogue for the (deoxy)ribose nucleic acids and in recent years has been the subject of several experimental and theoretical studies [4,5,6,7,8,9,10,11,12,13,14,15].

Methods

Results

Conclusion