Ultrafast and radiationless electronic excited state decay of uracil and thymine cations: computing the effects of dynamic electron correlation
File(s)PCCP_rev2.pdf (5.62 MB)
Accepted version
Author(s)
Segarra-Martí, Javier
Tran, Thierry
Bearpark, Michael J
Type
Journal Article
Abstract
In this article we characterise the radiationless decay of the first few electronic excited states of the cations of DNA/RNA nucleobases uracil and thymine, including the effects of dynamic electron correlation on energies and geometries (optimised with XMS-CASPT2). In both systems, we find that one state of 2n+O and another two of 2π+ character can be populated following photoionisation, and their different minima and interstate crossings are located. We find strong similarities between uracil and thymine cations: with accessible conical intersections suggesting that depopulation of their electronic excited states takes place on ultrafast timescales in both systems, suggesting that they are photostable in agreement with previous theoretical (uracil+) evidence. We find that dynamic electron correlation separates the energy levels of the "3-state" conical intersection (D2/D1/D0)CI previously located with CASSCF for uracil+, which will therefore have a different geometry and higher energy. Simulating the electronic and vibrational absorptions allows us to characterise spectral fingerprints that could be used to monitor these cation photo-processes experimentally.
Date Issued
2019-01-28
Date Acceptance
2019-01-22
Citation
Physical Chemistry Chemical Physics, 2019, 21 (26), pp.14322-14330
ISSN
1463-9076
Publisher
Royal Society of Chemistry
Start Page
14322
End Page
14330
Journal / Book Title
Physical Chemistry Chemical Physics
Volume
21
Issue
26
Copyright Statement
© the Owner Societies 2019.
Sponsor
European Commission
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/30698175
Grant Number
Marie Sklodowska Curie Actions (MSCA-IF)
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
2ND-ORDER PERTURBATION-THEORY
MOLECULAR WAVE-FUNCTIONS
ANO BASIS-SETS
CONICAL INTERSECTIONS
PHOTOELECTRON-SPECTROSCOPY
PYRIMIDINE NUCLEOSIDES
RELAXATION DYNAMICS
NUCLEIC-ACIDS
DNA
NUCLEOBASES
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
Publication Status
Published
Coverage Spatial
England
Date Publish Online
2019-01-28