Cargando…

A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex

A density matrix renormalization group‐self consistent field (DMRG‐SCF) study has been carried out to calculate the low‐lying excited states of CpMo(CO)(2)NO, a molybdenum complex containing NO and CO ligands. In order to automatically select an appropriate active space, a novel procedure employing...

Descripción completa

Detalles Bibliográficos
Autores principales: Freitag, Leon, Lindenbauer, Leopold, Oppel, Markus, González, Leticia
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9292996/
https://www.ncbi.nlm.nih.gov/pubmed/34495578
http://dx.doi.org/10.1002/cphc.202100549
_version_ 1784749511587921920
author Freitag, Leon
Lindenbauer, Leopold
Oppel, Markus
González, Leticia
author_facet Freitag, Leon
Lindenbauer, Leopold
Oppel, Markus
González, Leticia
author_sort Freitag, Leon
collection PubMed
description A density matrix renormalization group‐self consistent field (DMRG‐SCF) study has been carried out to calculate the low‐lying excited states of CpMo(CO)(2)NO, a molybdenum complex containing NO and CO ligands. In order to automatically select an appropriate active space, a novel procedure employing the maximum single‐orbital entropy for several states has been introduced and shown to be efficient and easy‐to‐implement when several electronic states are simultaneously considered. The analysis of the resulting natural transition orbitals and charge‐transfer numbers shows that the lowest five excited electronic states are excitation into metal‐NO antibonding orbitals, which offer the possibility for nitric oxide (NO) photorelease after excitation with visible light. Higher excited states are metal‐centered excitations with contributions of metal‐CO antibonding orbitals, which may serve as a gateway for carbon monoxide (CO) delivery. Time‐dependent density functional theory calculations done for comparison, show that the state characters agree remarkably well with those from DMRG‐SCF, while excitation energies are 0.4–1.0 eV red‐shifted with respect to the DMRG‐SCF ones.
format Online
Article
Text
id pubmed-9292996
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-92929962022-07-20 A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex Freitag, Leon Lindenbauer, Leopold Oppel, Markus González, Leticia Chemphyschem Articles A density matrix renormalization group‐self consistent field (DMRG‐SCF) study has been carried out to calculate the low‐lying excited states of CpMo(CO)(2)NO, a molybdenum complex containing NO and CO ligands. In order to automatically select an appropriate active space, a novel procedure employing the maximum single‐orbital entropy for several states has been introduced and shown to be efficient and easy‐to‐implement when several electronic states are simultaneously considered. The analysis of the resulting natural transition orbitals and charge‐transfer numbers shows that the lowest five excited electronic states are excitation into metal‐NO antibonding orbitals, which offer the possibility for nitric oxide (NO) photorelease after excitation with visible light. Higher excited states are metal‐centered excitations with contributions of metal‐CO antibonding orbitals, which may serve as a gateway for carbon monoxide (CO) delivery. Time‐dependent density functional theory calculations done for comparison, show that the state characters agree remarkably well with those from DMRG‐SCF, while excitation energies are 0.4–1.0 eV red‐shifted with respect to the DMRG‐SCF ones. John Wiley and Sons Inc. 2021-10-12 2021-11-18 /pmc/articles/PMC9292996/ /pubmed/34495578 http://dx.doi.org/10.1002/cphc.202100549 Text en © 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Articles
Freitag, Leon
Lindenbauer, Leopold
Oppel, Markus
González, Leticia
A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex
title A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex
title_full A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex
title_fullStr A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex
title_full_unstemmed A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex
title_short A Density Matrix Renormalization Group Study of the Low‐Lying Excited States of a Molybdenum Carbonyl‐Nitrosyl Complex
title_sort density matrix renormalization group study of the low‐lying excited states of a molybdenum carbonyl‐nitrosyl complex
topic Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9292996/
https://www.ncbi.nlm.nih.gov/pubmed/34495578
http://dx.doi.org/10.1002/cphc.202100549
work_keys_str_mv AT freitagleon adensitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex
AT lindenbauerleopold adensitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex
AT oppelmarkus adensitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex
AT gonzalezleticia adensitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex
AT freitagleon densitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex
AT lindenbauerleopold densitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex
AT oppelmarkus densitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex
AT gonzalezleticia densitymatrixrenormalizationgroupstudyofthelowlyingexcitedstatesofamolybdenumcarbonylnitrosylcomplex