Intramolecular surfaces for vicinal proton–proton coupling constants 3JHH

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Title: Intramolecular surfaces for vicinal proton–proton coupling constants 3JHH
Authors: Díez, Ernesto | Esteban, Ángel L. | San Fabián Maroto, Jesús | Galache Payá, María Paz | Casanueva, Jorge | Contreras, Rubén H.
Research Group/s: Grupo de Fotoquímica y Electroquímica de Semiconductores (GFES)
Center, Department or Service: Universidad de Alicante. Departamento de Química Física
Keywords: Vicinal coupling constants | Intramolecular surfaces | Vibrational contributions | Extended Karplus equations | DFT/B3LYP
Knowledge Area: Química Física
Issue Date: 3-Mar-2014
Publisher: Taylor & Francis
Citation: Molecular Physics. 2014, 112(16): 2138-2154. doi:10.1080/00268976.2014.891768
Abstract: Equations for the intramolecular surfaces of the 3JHH coupling constants in ethane, ethylene, and acetylene are formulated, and the corresponding coefficients are estimated from calculations at the DFT/B3LYP level. The chosen variables are changes in bond lengths, in the torsion angle φ between the coupled protons Ha and Hb, in bond angles, and in dihedral angles. The 3JHH surface of ethane is formulated as an extended Karplus equation with the coefficients of a truncated Fourier series on the torsion angle φ expanded as second-order Taylor series in the chosen variables taking into account the invariance of 3JHH under reflections and rotations of nuclear coordinates. Partial vibrational contributions from linear and square terms corresponding to changes in the geometry of the Ha − Ca − Cb − Hb fragment are important while those from cross terms are small with a few exceptions. The 3JHH surface of ethane is useful to predict contributions to 3JHH from changes in local geometry of derivatives but vibrational contributions are predicted less satisfactorily. The predicted values at the B3LYP/BS2 level of the 3JHH couplings (vibrational contributions at 300 K) from equilibrium geometries are 9.79 (−0.17) for acetylene, and 17.08 (1.93) and 10.73(0.93) for the trans and cis couplings of ethylene.
Sponsor: Financial support from the Dirección General de Enseñanza Superior e Investigación Científica (DGESIC), Spain [grant number CTQ2006-15141] is gratefully acknowledged. R.H. Contreras gratefully acknowledge financial support from Universidad de Buenos Aires Ciencia y Técnica UBACyT (2011–2013) and Consejo Nacional de Investigaciones Científicas y Técnicas CONICET [grant number PIP 0369/10].
URI: http://hdl.handle.net/10045/47836
ISSN: 0026-8976 (Print) | 1362-3028 (Online)
DOI: 10.1080/00268976.2014.891768
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2014 Taylor & Francis
Peer Review: si
Publisher version: http://dx.doi.org/10.1080/00268976.2014.891768
Appears in Collections:INV - GFES - Artículos de Revistas

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