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Multiconfigurational Effects in Theoretical Resonance Raman Spectra

We analyze resonance Raman spectra of the nucleobase uracil in the short‐time approximation calculated with multiconfigurational methods. We discuss the importance of static electron correlation by means of density‐matrix renormalization group self‐consistent field (DMRG‐SCF) calculations. Our DMRG‐...

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Detalles Bibliográficos
Autores principales: Ma, Yingjin, Knecht, Stefan, Reiher, Markus
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5324552/
https://www.ncbi.nlm.nih.gov/pubmed/27933695
http://dx.doi.org/10.1002/cphc.201601072
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author Ma, Yingjin
Knecht, Stefan
Reiher, Markus
author_facet Ma, Yingjin
Knecht, Stefan
Reiher, Markus
author_sort Ma, Yingjin
collection PubMed
description We analyze resonance Raman spectra of the nucleobase uracil in the short‐time approximation calculated with multiconfigurational methods. We discuss the importance of static electron correlation by means of density‐matrix renormalization group self‐consistent field (DMRG‐SCF) calculations. Our DMRG‐SCF results reveal that a minimal active orbital space that leads to a qualitatively correct description of the resonance Raman spectrum of uracil should encompass parts of the σ/σ* bonding/anti‐bonding orbitals of the pyrimidine ring. We trace these findings back to the considerable entanglement between the σ/σ* bonding/anti‐bonding as well as valence π/π* orbitals in the excited‐state electronic structure of uracil, which indicates non‐negligible non‐dynamical correlation effects that are less pronounced in the electronic ground state.
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spelling pubmed-53245522017-03-08 Multiconfigurational Effects in Theoretical Resonance Raman Spectra Ma, Yingjin Knecht, Stefan Reiher, Markus Chemphyschem Articles We analyze resonance Raman spectra of the nucleobase uracil in the short‐time approximation calculated with multiconfigurational methods. We discuss the importance of static electron correlation by means of density‐matrix renormalization group self‐consistent field (DMRG‐SCF) calculations. Our DMRG‐SCF results reveal that a minimal active orbital space that leads to a qualitatively correct description of the resonance Raman spectrum of uracil should encompass parts of the σ/σ* bonding/anti‐bonding orbitals of the pyrimidine ring. We trace these findings back to the considerable entanglement between the σ/σ* bonding/anti‐bonding as well as valence π/π* orbitals in the excited‐state electronic structure of uracil, which indicates non‐negligible non‐dynamical correlation effects that are less pronounced in the electronic ground state. John Wiley and Sons Inc. 2017-01-16 2017-02-17 /pmc/articles/PMC5324552/ /pubmed/27933695 http://dx.doi.org/10.1002/cphc.201601072 Text en © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs (http://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Articles
Ma, Yingjin
Knecht, Stefan
Reiher, Markus
Multiconfigurational Effects in Theoretical Resonance Raman Spectra
title Multiconfigurational Effects in Theoretical Resonance Raman Spectra
title_full Multiconfigurational Effects in Theoretical Resonance Raman Spectra
title_fullStr Multiconfigurational Effects in Theoretical Resonance Raman Spectra
title_full_unstemmed Multiconfigurational Effects in Theoretical Resonance Raman Spectra
title_short Multiconfigurational Effects in Theoretical Resonance Raman Spectra
title_sort multiconfigurational effects in theoretical resonance raman spectra
topic Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5324552/
https://www.ncbi.nlm.nih.gov/pubmed/27933695
http://dx.doi.org/10.1002/cphc.201601072
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