Solvent Effects on the Indirect Spin–Spin Coupling Constants of Benzene: The DFT-PCM Approach

International Journal of Molecular Sciences

Kenneth Ruud¹  Luca Frediani¹  Roberto Cammi¹ 

[1] ¹Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway ²Dipartimento di Chimica Generale ed Inorganica, Universit`a di Parma, viale delle Scienze, 43100 Parma, Italy <sup>3</sup>Dipartimento di Chimica e Chimica Industriale, Universit`a di Pisa, via Risorgimento 35, 56126 Pisa, Italy

关键词: Indirect spin–spin coupling constants;    Benzene;    Solvent effects;    Dielectric Medium;    PCM;   

DOI  :  10.3390/i4030119

来源: mdpi

【 摘 要 】

We present an extension of the Polarizable Continuum Model (PCM) to the calculation of solvent effects on indirect spin–spin coupling constants for Hartree–Fock wave functions and Density Functional Theory. This is achieved by implementing the PCM model for singlet and triplet linear response functions. The new code is used for calculating the solvent effects on the indirect spin–spin coupling constants of benzene. For the ¹J(H¹³C) coupling constants, our calculated solvent shifts are in good agreement with experimental observations when geometry relaxation is taken into account. However, our results do not support the extrapolated gas-phase value for this coupling constant. A new experimentally derived ¹J(H ¹³C) for a vibrating benzene molecule at 300 K is proposed.

【 授权许可】

CC BY   
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.