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  4. Characterizing Conical Intersections in DNA/RNA Nucleobases with Multiconfigurational Wave Functions of Varying Active Space Size
 
research article

Characterizing Conical Intersections in DNA/RNA Nucleobases with Multiconfigurational Wave Functions of Varying Active Space Size

Cuellar-Zuquin, Juliana
•
Pepino, Ana Julieta
•
Fdez Galvan, Ignacio
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October 26, 2023
Journal of Chemical Theory and Computation

We characterize the photochemically relevant conical intersections between the lowest-lying accessible electronic excited states of the different DNA/RNA nucleobases using Cholesky decomposition-based complete active space self-consistent field (CASSCF) algorithms. We benchmark two different basis set contractions and several active spaces for each nucleobase and conical intersection type, measuring for the first time how active space size affects conical intersection topographies in these systems and the potential implications these may have toward their description of photoinduced phenomena. Our results show that conical intersection topographies are highly sensitive to the electron correlation included in the model: by changing the amount (and type) of correlated orbitals, conical intersection topographies vastly change, and the changes observed do not follow any converging pattern toward the topographies obtained with the largest and most correlated active spaces. Comparison across systems shows analogous topographies for almost all intersections mediating population transfer to the dark (1)n(O/N)pi* states, while no similarities are observed for the "ethylene-like" conical intersection ascribed to mediate the ultrafast decay component to the ground state in all DNA/RNA nucleobases. Basis set size seems to have a minor effect, appearing to be relevant only for purine-based derivatives. We rule out structural changes as a key factor in classifying the different conical intersections, which display almost identical geometries across active space and basis set change, and we highlight instead the importance of correctly describing the electronic states involved at these crossing points. Our work shows that careful active space selection is essential to accurately describe conical intersection topographies and therefore to adequately account for their active role in molecular photochemistry.

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Type
research article
DOI
10.1021/acs.jctc.3c00577
Web of Science ID

WOS:001110588400001

Author(s)
Cuellar-Zuquin, Juliana
Pepino, Ana Julieta
Fdez Galvan, Ignacio
Rivalta, Ivan
Aquilante, Francesco  
Garavelli, Marco
Lindh, Roland
Segarra-Marti, Javier
Date Issued

2023-10-26

Publisher

Amer Chemical Soc

Published in
Journal of Chemical Theory and Computation
Volume

19

Issue

22

Start page

8258

End page

8272

Subjects

Physical Sciences

•

Potential-Energy Surfaces

•

Excited-State Dynamics

•

Ano Basis-Sets

•

Ab-Initio

•

Ultrafast Decay

•

Photoelectron-Spectroscopy

•

Radiationless Decay

•

Molecular-Dynamics

•

Coupling Vectors

•

3-State Model

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
THEOS  
FunderGrant Number

European Social Fund

100010434

La Caixa" Foundation

847648

European Union

RYC2021-034191-I

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Available on Infoscience
February 20, 2024
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/204457
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