solvent effects on the indirect spin–spin coupling constants of benzene the dft-pcm approach溶剂的影响间接自旋自旋耦合常数dft-pcm苯的方法.pdfVIP

Int. J. Mol. Sci. 2003, 4, 119-134 International Journal of Molecular Sciences ISSN 1422-0067 /ijms/ Solvent Effects on the Indirect Spin–Spin Coupling Constants of Benzene: The DFT-PCM Approach 1 2 2 3 Kenneth Ruud , Luca Frediani , Roberto Cammi , and Benedetta Mennucci 1 Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway. E-mail: ruud@chem.uit.no 2 Dipartimento di Chimica Generale ed Inorganica, Universit`a di Parma, viale delle Scienze, 43100 Parma, Italy 3 Dipartimento di Chimica e Chimica Industriale, Universit`a di Pisa, via Risorgimento 35, 56126 Pisa, Italy Received: 1 September 2002 / Accepted: 15 November 2002 / Published: 25 February 2003 Abstract: 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