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Title: On the Electronically Excited States of Uracil

Abstract

Vertical excitation energies in uracil in the gas phase and in water solution are investigated by the equation-of-motion coupled-cluster and multi-reference configuration interaction methods. Basis set effects are found to be important for converged results. The analysis of electronic wave functions reveals that the lowest singlet states are predominantly of a singly excited character and are therefore well described by single-reference equation-of-motion methods augmented by a perturbative triples correction to account for dynamical correlation. Our best estimates for the vertical excitation energies for the lowest singlet n and are 5.0±0.1 eV and 5.3±0.1 eV, respectively. The solvent effects for these states are estimated to be +0.5 eV and ±0.1 eV, respectively. We attribute the difference between the computed vertical excitations and the maximum of the experimental absorption to strong vibronic interaction between the lowest A00 and A0 states leading to intensity borrowing by the forbidden transition.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
946631
Report Number(s):
PNNL-SA-60634
400403309; TRN: US200903%%439
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A, 112(40):9983-9992
Additional Journal Information:
Journal Volume: 112; Journal Issue: 40
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; EXCITATION; EXCITED STATES; FORBIDDEN TRANSITIONS; URACILS; WAVE FUNCTIONS

Citation Formats

Epifanovsky, Evgeny, Kowalski, Karol, Fan, Peng-Dong, Valiev, Marat, Matsika, Spiridoula, and Krylov, Anna. On the Electronically Excited States of Uracil. United States: N. p., 2008. Web. doi:10.1021/jp803758q.
Epifanovsky, Evgeny, Kowalski, Karol, Fan, Peng-Dong, Valiev, Marat, Matsika, Spiridoula, & Krylov, Anna. On the Electronically Excited States of Uracil. United States. https://doi.org/10.1021/jp803758q
Epifanovsky, Evgeny, Kowalski, Karol, Fan, Peng-Dong, Valiev, Marat, Matsika, Spiridoula, and Krylov, Anna. 2008. "On the Electronically Excited States of Uracil". United States. https://doi.org/10.1021/jp803758q.
@article{osti_946631,
title = {On the Electronically Excited States of Uracil},
author = {Epifanovsky, Evgeny and Kowalski, Karol and Fan, Peng-Dong and Valiev, Marat and Matsika, Spiridoula and Krylov, Anna},
abstractNote = {Vertical excitation energies in uracil in the gas phase and in water solution are investigated by the equation-of-motion coupled-cluster and multi-reference configuration interaction methods. Basis set effects are found to be important for converged results. The analysis of electronic wave functions reveals that the lowest singlet states are predominantly of a singly excited character and are therefore well described by single-reference equation-of-motion methods augmented by a perturbative triples correction to account for dynamical correlation. Our best estimates for the vertical excitation energies for the lowest singlet n and are 5.0±0.1 eV and 5.3±0.1 eV, respectively. The solvent effects for these states are estimated to be +0.5 eV and ±0.1 eV, respectively. We attribute the difference between the computed vertical excitations and the maximum of the experimental absorption to strong vibronic interaction between the lowest A00 and A0 states leading to intensity borrowing by the forbidden transition.},
doi = {10.1021/jp803758q},
url = {https://www.osti.gov/biblio/946631}, journal = {Journal of Physical Chemistry A, 112(40):9983-9992},
number = 40,
volume = 112,
place = {United States},
year = {Thu Oct 09 00:00:00 EDT 2008},
month = {Thu Oct 09 00:00:00 EDT 2008}
}