title: Calculation of nuclear spin-spin coupling constants using frozen density embedding.
abstract: We present a method for a subsystem-based calculation of indirect nuclear spin-spin coupling tensors within the framework of current-spin-density-functional theory. Our approach is based on the frozen-density embedding scheme within density-functional theory and extends a previously reported subsystem-based approach for the calculation of nuclear magnetic resonance shielding tensors to magnetic fields which couple not only to orbital but also spin degrees of freedom. This leads to a formulation in which the electron density, the induced paramagnetic current, and the induced spin-magnetization density are calculated separately for the individual subsystems. This is particularly useful for the inclusion of environmental effects in the calculation of nuclear spin-spin coupling constants. Neglecting the induced paramagnetic current and spin-magnetization density in the environment due to the magnetic moments of the coupled nuclei leads to a very efficient method in which the computationally expensive response calculation has to be performed only for the subsystem of interest. We show that this approach leads to very good results for the calculation of solvent-induced shifts of nuclear spin-spin coupling constants in hydrogen-bonded systems. Also for systems with stronger interactions, frozen-density embedding performs remarkably well, given the approximate nature of currently available functionals for the non-additive kinetic energy. As an example we show results for methylmercury halides which exhibit an exceptionally large shift of the one-bond coupling constants between (199)Hg and (13)C upon coordination of dimethylsulfoxide solvent molecules.
authors.affiliation: San Diego Supercomputer Center, University of California San Diego, 9500 Gilman Dr MC 0505, La Jolla, California 92093-0505, USA.
authors.forename: Andreas W
authors.initials: AW
authors.lastname: Götz
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260-3000, USA.
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach
authors.affiliation: Amsterdam Center for Multiscale Modeling (ACMM), VU University Amsterdam, Theoretical Chemistry, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
authors.forename: Lucas
authors.initials: L
authors.lastname: Visscher
mesh_terms: D000465:Algorithms; D000641:Ammonia / Q000737:chemistry; D002247:Carbon Isotopes / Q000737:chemistry; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004583:Electrons; D006858:Hydrofluoric Acid / Q000737:chemistry; D006860:Hydrogen Bonding; D007700:Kinetics; D060526:Magnetic Fields; D009682:Magnetic Resonance Spectroscopy; D008629:Mercury Isotopes / Q000737:chemistry; D008767:Methylmercury Compounds / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D012984:Software; D012997:Solvents / Q000737:chemistry; D014867:Water / Q000737:chemistry
chemical_list: D002247:Carbon Isotopes; D008629:Mercury Isotopes; D008767:Methylmercury Compounds; D012997:Solvents; D014867:Water; D000641:Ammonia; D006858:Hydrofluoric Acid; D004121:Dimethyl Sulfoxide