Solvent Effect on the NMR Chemical Shieldings in Water Calculated by a Combination of Molecular Dynamics and Density Functional Theory

The solvent effect on the NMR chemical shielding in liquid water is calculated from a combination of molecular dynamics simulations and quantum chemical calculations for protons and 17O. The simulations are performed with three different potentials, ab initio as well as empirical ones, to study the influence of the force field. From the liquid configurations obtained in these simulations, molecules are randomly chosen together with neighbouring molecules to give clusters of water typical for the liquid at the selected temperature and density. Different cluster sizes are studied. The clusters are treated as supermolecules in quantum chemical calculations of chemical shifts by sum-over-states density functional perturbation theory with individual gauge for localised orbitals. The influence of the quantum chemical method is studied with an ab initio coupled Hartree-Fock gauge including atomic orbitals calculations with different basis sets for a selected cluster. An average over clusters yields the chemical shielding in the liquid at the selected temperature and density. The calculated values for the gas–liquid shift, which are in best agreement with experiment, are –3.2 ppm (exp. –4.26 ppm) for the proton and –37.6 ppm (exp. –36.1 ppm) for 17O, but the results depend strongly on the chosen interatomic potential.

[1]  J. Hindman,et al.  Proton Resonance Shift of Water in the Gas and Liquid States , 1966 .

[2]  A. Florin,et al.  17O NMR Shifts in H217O Liquid and Vapor , 1967 .

[3]  G. Govil Nuclear magnetic resonance studies in gases , 1973 .

[4]  G. D. Carney,et al.  Improved potential functions for bent AB2 molecules: Water and ozone , 1976 .

[5]  Frank H. Stillinger,et al.  Revised central force potentials for water , 1978 .

[6]  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 .

[7]  K. Heinzinger,et al.  An improved potential for non-rigid water molecules in the liquid phase , 1983 .

[8]  W. T. Raynes The 17O nuclear magnetic shielding in H2 17O and D2 17O , 1983 .

[9]  Lie,et al.  Molecular-dynamics simulation of liquid water with an ab initio flexible water-water interaction potential. , 1986, Physical review. A, General physics.

[10]  B. Montgomery Pettitt,et al.  Simple intramolecular model potentials for water , 1987 .

[11]  J. Banavar,et al.  Computer Simulation of Liquids , 1988 .

[12]  D. Salahub,et al.  New algorithm for the optimization of geometries in local density functional theory , 1990 .

[13]  Ulrich Fleischer,et al.  The IGLO-Method: Ab-initio Calculation and Interpretation of NMR Chemical Shifts and Magnetic Susceptibilities , 1990 .

[14]  Cynthia J. Jameson Gas-phase NMR spectroscopy , 1991 .

[15]  K. Hermansson,et al.  THE OH VIBRATIONAL-SPECTRUM OF LIQUID WATER FROM COMBINED ABINITIO AND MONTE-CARLO CALCULATIONS , 1991 .

[16]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[17]  R. Eggenberger,et al.  Ab initio calculation of the deuterium quadrupole coupling in liquid water , 1992 .

[18]  L. Ojamäe,et al.  The OH stretching frequency in liquid water simulations: the classical error , 1992 .

[19]  J. F. Hinton,et al.  Ab initio quantum mechanical calculation of the chemical shift anisotropy of the hydrogen atom in the (H2O)17 water cluster , 1992 .

[20]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[21]  R. Eggenberger,et al.  The use of molecular dynamics simulations with ab initio SCF calculations for the determination of the oxygen-17 quadrupole coupling constant in liquid water , 1993 .

[22]  P. Kusalik,et al.  Proton chemical shift of water in the liquid state: computer simulation results , 1993 .

[23]  J. F. Hinton,et al.  Hartree–Fock and second‐order Mo/ller–Plesset perturbation theory calculations of the 31P nuclear magnetic resonance shielding tensor in PH3 , 1993 .

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

[25]  Rolf Eggenberger,et al.  Use of molecular dynamics simulations with ab initio SCF calculations for the determination of the deuterium quadrupole coupling constant in liquid water and bond lengths in ice , 1993, J. Comput. Chem..

[26]  L. Ojamäe,et al.  THEORETICAL SIMULATION OF OH AND OD STRETCHING BANDS OF ISOTOPICALLY DILUTED HDO MOLECULES IN AQUEOUS-SOLUTION , 1993 .

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

[28]  D. B. Chesnut,et al.  A study of NMR chemical shielding in water clusters derived from molecular dynamics simulations , 1994 .

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

[30]  Paul von Ragué Schleyer,et al.  Interrelationship between Conformation and Theoretical Chemical Shifts. Case Study on Glycine and Glycine Amide , 1994 .

[31]  Peter Politzer,et al.  Modern density functional theory: a tool for chemistry , 1995 .

[32]  Influence of the Nonplanarity of the Amide Moiety on Computed Chemical Shifts in Peptide Analogs. Is the Amide Nitrogen Pyramidal , 1995 .

[33]  D. Salahub,et al.  INFLUENCE OF INTERMOLECULAR INTERACTIONS ON THE 13C NMR SHIELDING TENSOR IN SOLID ALPHA -GLYCINE , 1995 .

[34]  B. Roux,et al.  The backbone 15N chemical shift tensor of the gramicidin channel. A molecular dynamics and density functional study , 1995 .

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