Assessment of the potential energy hypersurfaces in thymine within multiconfigurational theory: CASSCF vs. CASPT2
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Published version
Author(s)
Segarra-Marti, Javier
Frances-Monerris, Antonio
Roca-Sanjuan, Daniel
Merchan, Manuela
Type
Journal Article
Abstract
The present study provides new insights into the topography of the potential energy hypersurfaces (PEHs) of the thymine nucleobase in order to rationalize its main ultrafast photochemical decay paths by employing two methodologies based on the complete active space self-consistent field (CASSCF) and the complete active space second-order perturbation theory (CASPT2) methods: (i) CASSCF optimized structures and energies corrected with the CASPT2 method at the CASSCF geometries and (ii) CASPT2 optimized geometries and energies. A direct comparison between these strategies is drawn, yielding qualitatively similar results within a static framework. A number of analyses are performed to assess the accuracy of these different computational strategies under study based on a variety of numerical thresholds and optimization methods. Several basis sets and active spaces have also been calibrated to understand to what extent they can influence the resulting geometries and subsequent interpretation of the photochemical decay channels. The study shows small discrepancies between CASSCF and CASPT2 PEHs, displaying a shallow planar or twisted 1(ππ*) minimum, respectively, and thus featuring a qualitatively similar scenario for supporting the ultrafast bi-exponential deactivation registered in thymine upon UV-light exposure. A deeper knowledge of the PEHs at different levels of theory provides useful insight into its correct characterization and subsequent interpretation of the experimental observations. The discrepancies displayed by the different methods studied here are then discussed and framed within their potential consequences in on-the-fly non-adiabatic molecular dynamics simulations, where qualitatively diverse outcomes are expected.
Date Issued
2016-12-03
Date Acceptance
2016-12-01
Citation
Molecules, 2016, 21 (12)
ISSN
1420-3049
Publisher
MDPI AG
Journal / Book Title
Molecules
Volume
21
Issue
12
Copyright Statement
© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
License URL
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000392140100060&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Life Sciences & Biomedicine
Physical Sciences
Biochemistry & Molecular Biology
Chemistry, Multidisciplinary
Chemistry
CASSCF/CASPT2
photochemistry
DNA
thymine
photostability
EXCITED-STATE DYNAMICS
2ND-ORDER PERTURBATION-THEORY
2-DIMENSIONAL ELECTRONIC SPECTROSCOPY
ULTRAFAST INTERNAL-CONVERSION
RETINAL CHROMOPHORE MODEL
INITIO MOLECULAR-DYNAMICS
COUPLED-CLUSTER METHODS
LOWEST TRIPLET-STATE
ANO BASIS-SETS
AB-INITIO
Publication Status
Published
Article Number
ARTN 1666