The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters

Polarization propagators (PP) are powerful theoretical tools that allow carrying out a deep analysis of the electronic mechanisms underlying any molecular response property. The inner projections of the PP and contributions from localized orbitals within the PP approaches described in Section 2 were...

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Autores principales: Aucar, Gustavo A., Ruiz de Azúa, Martín César, Giribet, Claudia Gloria
Publicado: 2013
Materias:
CLOPPA method
Karplus rule
Localized orbitals and NMR parameters
Polarization propagators in NMR
Transmission mechanisms of NMR J couplings
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_18754023_v3_n1_p119_Aucar
http://hdl.handle.net/20.500.12110/paper_18754023_v3_n1_p119_Aucar
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_18754023_v3_n1_p119_Aucar
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spelling paper:paper_18754023_v3_n1_p119_Aucar2023-06-08T16:30:10Z The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters Aucar, Gustavo A. Ruiz de Azúa, Martín César Giribet, Claudia Gloria CLOPPA method Karplus rule Localized orbitals and NMR parameters Polarization propagators in NMR Transmission mechanisms of NMR J couplings Polarization propagators (PP) are powerful theoretical tools that allow carrying out a deep analysis of the electronic mechanisms underlying any molecular response property. The inner projections of the PP and contributions from localized orbitals within the PP approaches described in Section 2 were developed to fully take advantage of this power of analysis for the study of NMR spectroscopic parameters. They are based on the use of localized molecular orbitals (LMOs) related to chemically intuitive concepts to decompose the mathematical expression of these parameters into coupling pathways or shielding pathways. Each of them may be furthermore decomposed into two new objects: (i) perturbators, which give information on the efficiency of a given magnetic perturbation to produce local excitations and (ii) the principal propagator matrix elements which provide deep understanding on the way perturbations are transmitted within the electronic framework of the molecule under study. Applications are presented in Section 3, both within semiempirical and ab initio approaches: the Karplus rule, a general analysis of the signs of J couplings, σ-π decomposition, hyperconjugative effects in transmission of J couplings, general features of 1J couplings, and intermolecular couplings in hydrogen-bonded systems. All applications were especially selected to cover examples in which qualitative physical insight can be gained. © 2013 Elsevier B.V. Fil:Aucar, G.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Ruiz de Azúa, M.C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Giribet, C.G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2013 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_18754023_v3_n1_p119_Aucar http://hdl.handle.net/20.500.12110/paper_18754023_v3_n1_p119_Aucar
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic CLOPPA method
Karplus rule
Localized orbitals and NMR parameters
Polarization propagators in NMR
Transmission mechanisms of NMR J couplings
spellingShingle CLOPPA method
Karplus rule
Localized orbitals and NMR parameters
Polarization propagators in NMR
Transmission mechanisms of NMR J couplings
Aucar, Gustavo A.
Ruiz de Azúa, Martín César
Giribet, Claudia Gloria
The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters
topic_facet CLOPPA method
Karplus rule
Localized orbitals and NMR parameters
Polarization propagators in NMR
Transmission mechanisms of NMR J couplings
description Polarization propagators (PP) are powerful theoretical tools that allow carrying out a deep analysis of the electronic mechanisms underlying any molecular response property. The inner projections of the PP and contributions from localized orbitals within the PP approaches described in Section 2 were developed to fully take advantage of this power of analysis for the study of NMR spectroscopic parameters. They are based on the use of localized molecular orbitals (LMOs) related to chemically intuitive concepts to decompose the mathematical expression of these parameters into coupling pathways or shielding pathways. Each of them may be furthermore decomposed into two new objects: (i) perturbators, which give information on the efficiency of a given magnetic perturbation to produce local excitations and (ii) the principal propagator matrix elements which provide deep understanding on the way perturbations are transmitted within the electronic framework of the molecule under study. Applications are presented in Section 3, both within semiempirical and ab initio approaches: the Karplus rule, a general analysis of the signs of J couplings, σ-π decomposition, hyperconjugative effects in transmission of J couplings, general features of 1J couplings, and intermolecular couplings in hydrogen-bonded systems. All applications were especially selected to cover examples in which qualitative physical insight can be gained. © 2013 Elsevier B.V.
author Aucar, Gustavo A.
Ruiz de Azúa, Martín César
Giribet, Claudia Gloria
author_facet Aucar, Gustavo A.
Ruiz de Azúa, Martín César
Giribet, Claudia Gloria
author_sort Aucar, Gustavo A.
title The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters
title_short The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters
title_full The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters
title_fullStr The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters
title_full_unstemmed The Polarization propagator approach as a tool to study electronic molecular structures from high-resolution NMR parameters
title_sort polarization propagator approach as a tool to study electronic molecular structures from high-resolution nmr parameters
publishDate 2013
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_18754023_v3_n1_p119_Aucar
http://hdl.handle.net/20.500.12110/paper_18754023_v3_n1_p119_Aucar
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