Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality

Azúa, Martín C. Ruiz de; Giribet, C. G.; Vizioli, C.; Contreras, Rubén H.

doi:10.1016/s0166-1280(98)00020-7

Cited by 28 publications

(36 citation statements)

References 28 publications

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“…We will start defining one of the most important semiempirical models, which was dubbed ''contributions from localized orbitals within polarization propagator approach'', (CLOPPA). This scheme was largely applied during the last decade by professor Contreras group on light-atom containing molecules, then extended by us and some collaborators together with professor Contreras to heavy-atom containing molecules; and then their main ideas were also extended to DFT and ab initio methods (62).…”

Section: Models and Applicationsmentioning

confidence: 99%

Understanding NMR J‐couplings by the theory of polarization propagators

Aucar

2008

Concepts Magnetic Resonance

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Propagators are powerful theoretical tools that were first developed within the nonrelativistic (NR) regime and were applied to calculate atomic and molecular properties more than 30 years ago. The recent relativistic generalization of polarization propagators has shown that these propagators play a special role in describing the quantum origin of any molecular property and the broad implication of their particular definition. In this article, we give a general overview on fundamentals and applications of polarization propagators to one of the most important NMR spectroscopic parameters, the nuclear spin coupling mediated by the electronic system within both regimes: relativistic and NR. This presentation is given in a level that can be followed with a basic knowledge of quantum mechanics. Our aim is to show what one can learn about molecular electronic configurations, and also the transmission and influence of magnetic perturbations on electronic systems from basic theoretical elements like molecular orbitals, electronic excitation energies, coupling pathways, entanglement, etc. by using propagators. We shall use i) semiempirical models and ii) ab initio calculations at different levels of approach. We give a deep insight on the electronic origin of the Karplus' rule, the sign of indirect nuclear spin couplings, unusually large long-range couplings, cooperativity effects, relativistic effects, and the origin of diamagnetism. Some of these analysis are based on previous publications, and some others are presented here for the first ime.

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Section: Models and Applicationsmentioning

confidence: 99%

Understanding NMR J‐couplings by the theory of polarization propagators

Aucar

2008

Concepts Magnetic Resonance

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“…It was implemented at the ab initio level for the theoretical analysis of NMR spin-spin couplings [10][11][12][13][14][15][16] and the static molecular polarizability tensor. 17,14,15 This method was applied to study, for instance, one-bond C-H couplings in complex systems with C-H‚‚‚O interactions, 17 and, very recently, to determine the electronic mechanisms which give rise to 1h J(A,H) and 2h J(A,D) couplings across D-H‚‚‚A hydrogen bonds in a set of small model compounds.…”

Section: Introductionmentioning

confidence: 99%

The Sign and Magnitude of ^2hJ(F,F) and ^1hJ(F,H) in FH···FH. A CLOPPA Analysis of Their Distance Dependence

Giribet

Azúa

2006

J. Phys. Chem. A

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The sign change of the intermolecular (2h)J(F,F) coupling in the (HF)2 dimer as a function of the F-F distance is discussed by means of the CLOPPA method. It is found that it is due to the competition of positive and negative contributions involving the interaction of the sigma lone pair of the acceptor nucleus with vacant molecular orbitals localized in the F-H...F moiety and with other molecular orbitals localized in the donor molecule. The origin of the sign of each contribution is fully determined by analyzing the response of the electronic system to the magnetic perturbation at the acceptor F nucleus. (2h)J(F,F) coupling in the FH...F-, which is positive for all F-F distances, is also analyzed in order to look for the differences with the former case.

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“…41 Consider an FC-like operator V j M which connects the j occupied LMO with the vacant LMOs (b*) at the site of nucleus M:…”

Section: Introductionmentioning

confidence: 99%

CLOPPA-IPPP Analysis of Electronic Mechanisms of Intermolecular ^1hJ(A,H) and ^2hJ(A,D) Spin−Spin Coupling Constants in Systems with D−H···A Hydrogen Bonds

Giribet

Azúa

2005

J. Phys. Chem. A

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The electronic origin of intermolecular (2h)J(A,D) and (1h)J(A,H) couplings is discussed by means of the CLOPPA-IPPP approach in several model complexes with D-H...A hydrogen bonds. It is found that the origin of these couplings is mainly due to the interaction between the acceptor sigma lone pair and vacant molecular orbitals localized in the D-H...A moiety, regardless of the donor and acceptor nuclei. The problem of the larger absolute value of (2h)J(A,D) compared to (1h)J(A,H) is also addressed.

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Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality

Cited by 28 publications

References 28 publications

Understanding NMR J‐couplings by the theory of polarization propagators

Understanding NMR J‐couplings by the theory of polarization propagators

The Sign and Magnitude of ^2hJ(F,F) and ^1hJ(F,H) in FH···FH. A CLOPPA Analysis of Their Distance Dependence

CLOPPA-IPPP Analysis of Electronic Mechanisms of Intermolecular ^1hJ(A,H) and ^2hJ(A,D) Spin−Spin Coupling Constants in Systems with D−H···A Hydrogen Bonds

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Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality

Cited by 28 publications

References 28 publications

Understanding NMR J‐couplings by the theory of polarization propagators

Understanding NMR J‐couplings by the theory of polarization propagators

The Sign and Magnitude of 2hJ(F,F) and 1hJ(F,H) in FH···FH. A CLOPPA Analysis of Their Distance Dependence

CLOPPA-IPPP Analysis of Electronic Mechanisms of Intermolecular 1hJ(A,H) and 2hJ(A,D) Spin−Spin Coupling Constants in Systems with D−H···A Hydrogen Bonds

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Product

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The Sign and Magnitude of ^2hJ(F,F) and ^1hJ(F,H) in FH···FH. A CLOPPA Analysis of Their Distance Dependence

CLOPPA-IPPP Analysis of Electronic Mechanisms of Intermolecular ^1hJ(A,H) and ^2hJ(A,D) Spin−Spin Coupling Constants in Systems with D−H···A Hydrogen Bonds