On the calculation of hydrogen NMR chemical shielding

Abstract Ab initio calculations of hydrogen NMR chemical shielding have been carried out at the correlation-including GIAO MP2 level on nine small molecules whose gas phase isotropic shieldings are well known. A range of basis sets from very small to rather large has been studied. While correlation effects at this level of theory are small, basis set and rovibrational effects are large. Large basis sets and the inclusion of rovibrational effects are necessary to calculate hydrogen shieldings well on an absolute basis (chemical shieldings), while the constraints are less demanding for calculations on a relative scale (chemical shifts) where agreement with experiment for the set of molecules studied as measured by the standard error is 0.11 ppm.

[1]  D. M. Bishop,et al.  Vibrational corrections for some electric and magnetic properties of H2, N2, HF, and CO , 1994 .

[2]  G. Schreckenbach,et al.  Calculation of NMR Shielding Tensors Using Gauge-Including Atomic Orbitals and Modern Density Functional Theory , 1995 .

[3]  W. Kutzelnigg,et al.  Ab Initio Computation of 77Se NMR Chemical Shifts with the IGLO-SCF, the GIAO-SCF, and the GIAO-MP2 Methods , 1995 .

[4]  W. Kutzelnigg,et al.  Calculation of nuclear magnetic resonance shieldings and magnetic susceptibilities using multiconfiguration Hartree–Fock wave functions and local gauge origins , 1996 .

[5]  J. Gauss.  GIAO-MBPT(3) and GIAO-SDQ-MBPT(4) calculations of nuclear magnetic shielding constants , 1994 .

[6]  Warren J. Hehre,et al.  AB INITIO Molecular Orbital Theory , 1986 .

[7]  C. D. Cornwell,et al.  Vibrational Corrections to the Nuclear‐Magnetic Shielding and Spin–Rotation Constants for Hydrogen Fluoride. Shielding Scale for 19F , 1968 .

[8]  P. Fowler,et al.  The effects of rotation, vibration and isotopic substitution on the electric dipole moment, the magnetizability and the nuclear magnetic shielding of the water molecule , 1981 .

[9]  H. Osten,et al.  The dependence of the 13C and the 1H nuclear magnetic shielding on bond extension in methane , 1984 .

[10]  W. Kutzelnigg,et al.  The MC-IGLO method , 1993 .

[11]  Robert L. Kuczkowski,et al.  Molecular structures of gas‐phase polyatomic molecules determined by spectroscopic methods , 1979 .

[12]  D. B. Chesnut,et al.  Use of locally dense basis sets for nuclear magnetic resonance shielding calculations , 1993, J. Comput. Chem..

[13]  H. Fukui,et al.  Calculation of nuclear magnetic shieldings. IX. Electron correlation effects , 1994 .

[14]  A. Jameson,et al.  Nuclear magnetic shielding of nitrogen in ammonia , 1991 .

[15]  J. Gauss.  Effects of electron correlation in the calculation of nuclear magnetic resonance chemical shifts , 1993 .

[16]  D. B. Chesnut,et al.  Locally dense basis sets for chemical shift calculations , 1989 .

[17]  R. Ditchfield.  Theoretical studies of the temperature dependence of magnetic shielding tensors: H2, HF, and LiH , 1981 .

[18]  John F. Stanton,et al.  Perturbative treatment of triple excitations in coupled‐cluster calculations of nuclear magnetic shielding constants , 1996 .

[19]  Dennis R. Salahub,et al.  NUCLEAR MAGNETIC RESONANCE SHIELDING TENSORS CALCULATED WITH A SUM-OVER-STATES DENSITY FUNCTIONAL PERTURBATION THEORY , 1994 .

[20]  H. Osten,et al.  Rovibrational averaging of molecular magnetic properties of CH3F, CH2F2, and CHF3 , 1985 .

[21]  R. Ditchfield,et al.  Self-consistent perturbation theory of diamagnetism , 1974 .

[22]  John F. Stanton,et al.  Gauge‐invariant calculation of nuclear magnetic shielding constants at the coupled–cluster singles and doubles level , 1995 .

[23]  J. Tossell,et al.  Nuclear magnetic shieldings and molecular structure , 1993 .

[24]  Hans W. Horn,et al.  Fully optimized contracted Gaussian basis sets for atoms Li to Kr , 1992 .

[25]  D. M. Bishop,et al.  Electron-correlated calculations of the nuclear shielding constants and shielding polarizabilities for H2, N2, HF and CO , 1993 .

[26]  D. B. Chesnut,et al.  Chemical shift bond derivatives for molecules containing first‐row atoms , 1991 .

[27]  Nicholas C. Handy,et al.  The density functional calculation of nuclear shielding constants using London atomic orbitals , 1995 .

[28]  W. G. Schneider,et al.  Proton Magnetic Resonance Chemical Shift of Free (Gaseous) and Associated (Liquid) Hydride Molecules , 1958 .

[29]  J. Gauss,et al.  [Ga(C5H5)]: Synthesis, Identification, and Ab Initio Investigations† , 1992 .

[30]  J. Gauss,et al.  Accurate computations of 77Se NMR chemical shifts with the GIAO-CCSD method , 1995 .

[31]  D. M. Bishop,et al.  Calculations of magnetic properties. II. Electron‐correlated nuclear shielding constants for nine small molecules , 1993 .

[32]  A. Jameson,et al.  Gas-phase 13C chemical shifts in the zero-pressure limit: refinements to the absolute shielding scale for 13C , 1987 .

[33]  J. D. Augspurger,et al.  Electromagnetic properties of molecules from a uniform procedure for differentiation of molecular wave functions to high order , 1991 .

[34]  Trygve Helgaker,et al.  Multiconfigurational self-consistent field calculations of nuclear shieldings using London atomic orbitals , 1994 .

[35]  P. Pulay,et al.  Basis set and correlation effects in the calculation of selenium NMR shieldings , 1994 .

[36]  J. Gauss.  Calculation of NMR chemical shifts at second-order many-body perturbation theory using gauge-including atomic orbitals , 1992 .

[37]  John F. Stanton,et al.  Coupled-cluster calculations of nuclear magnetic resonance chemical shifts , 1967 .

[38]  Guntram Rauhut,et al.  Comparison of NMR Shieldings Calculated from Hartree−Fock and Density Functional Wave Functions Using Gauge-Including Atomic Orbitals , 1996 .

[39]  H. Fukui,et al.  Calculation of nuclear magnetic shieldings. VIII: Gauge invariant many-body perturbation method , 1992 .