Nuclear magnetic resonance J coupling constant polarizabilities of hydrogen peroxide: A basis set and correlation study

In this article, we present the so far most extended investigation of the calculation of the coupling constant polarizability of a molecule. The components of the coupling constant polarizability are derivatives of the nuclear magnetic resonance (NMR) indirect nuclear spin–spin coupling constant with respect to an external electric field and play an important role for both chiral discrimination and solvation effects on NMR coupling constants. In this study, we illustrate the effects of one‐electron basis sets and electron correlation both at the level of density functional theory as well as second‐order polarization propagator approximation for the small molecule hydrogen peroxide, which allowed us to perform calculations with the largest available basis sets optimized for the calculation of NMR coupling constants. We find a systematic but rather slow convergence with the one‐electron basis set and that augmentation functions are required. We observe also large and nonsystematic correlation effects with significant differences between the density functional and wave function theory methods. © 2012 Wiley Periodicals, Inc.

[1]  J. Elguero,et al.  A Systematic Comparison of Second-Order Polarization Propagator Approximation (SOPPA) and Equation-of-Motion Coupled Cluster Singles and Doubles (EOM-CCSD) Spin-Spin Coupling Constants for Selected Singly Bonded Molecules, and the Hydrides NH3, H2O, and HF and Their Protonated and Deprotonated Ions , 2008, Journal of chemical theory and computation.

[2]  M. Pecul,et al.  Electric field effects on the shielding constants of noble gases: a four-component relativistic Hartree-Fock study. , 2004, The Journal of chemical physics.

[3]  F. Jensen.  The optimum contraction of basis sets for calculating spin–spin coupling constants , 2010 .

[4]  A. Soncini,et al.  Response tensors for chiral discrimination in NMR spectroscopy , 2008 .

[5]  A. Barra,et al.  PARITY NON-CONSERVATION AND NMR PARAMETERS , 1996 .

[6]  G. Scuseria,et al.  Basis set dependence of NMR spin–spin couplings in density functional theory calculations: first row and hydrogen atoms , 2003 .

[7]  J. Pople,et al.  CORRIGENDUM: Theoretical Studies of the Kerr Effect: I - Deviations from a Linear Polarization Law , 1955 .

[8]  K. Ruud,et al.  MCSCF calculations of hypermagnetizabilities and nuclear shielding polarizabilities of CO and CH4 , 1996 .

[9]  M. Grayson.  Electric Field Effects on 2JHH Spin-Spin Coupling Constants , 2003 .

[10]  J. Gauss,et al.  Shielding polarizabilities calculated at the coupled-cluster singles and doubles level augmented by a perturbative treatment of triple excitations , 2002 .

[11]  I. Mazin,et al.  Theory , 1934 .

[12]  A. D. Buckingham,et al.  CHEMICAL SHIFTS IN THE NUCLEAR MAGNETIC RESONANCE SPECTRA OF MOLECULES CONTAINING POLAR GROUPS , 1960 .

[13]  W. T. Raynes,et al.  Linear and quadratic electric-field dependence of the nuclear magnetic shielding in the hydrogen molecule , 1976 .

[14]  J. Kongsted,et al.  Benchmarking SOPPA(CC2) for the calculation of indirect nuclear spin-spin coupling constants: Carbocycles , 2011 .

[15]  Trygve Helgaker,et al.  Analytical calculation of nuclear magnetic resonance indirect spin–spin coupling constants at the generalized gradient approximation and hybrid levels of density-functional theory , 2000 .

[16]  S. Sauer,et al.  Structural trends of 77Se1H spin–spin coupling constants and conformational behavior of 2‐substituted selenophenes , 2010, Magnetic resonance in chemistry : MRC.

[17]  H. Ågren,et al.  Indirect nuclear spin–spin coupling constants from multiconfiguration linear response theory , 1992 .

[18]  P. Provasi,et al.  Optimized basis sets for the calculation of indirect nuclear spin-spin coupling constants involving the atoms B, Al, Si, P, and Cl. , 2010, The Journal of chemical physics.

[19]  S. Sauer,et al.  The computation of Karplus equation coefficients and their components using self-consistent field and second-order polarization propagator methods , 2000 .

[20]  Poul Jo,et al.  Transition moments and dynamic polarizabilities in a second order polarization propagator approach , 1980 .

[21]  James R Cheeseman,et al.  Calculation of Nuclear Spin-Spin Coupling Constants of Molecules with First and Second Row Atoms in Study of Basis Set Dependence. , 2006, Journal of chemical theory and computation.

[22]  Erratum to: Electric field effects on nuclear spin–spin coupling tensors and chiral discrimination via NMR spectroscopy , 2011 .

[23]  J. Kongsted,et al.  Optimized Basis Sets for Calculation of Electron Paramagnetic Resonance Hyperfine Coupling Constants: aug-cc-pVTZ-J for the 3d Atoms Sc-Zn. , 2011, Journal of chemical theory and computation.

[24]  S. Sauer,et al.  Unexpected differential sensitivity of nuclear spin–spin-coupling constants to bond stretching in BH4−, NH4+, and SiH4 , 2000 .

[25]  Stephan P. A. Sauer,et al.  Molecular Electromagnetism: A Computational Chemistry Approach , 2011 .

[26]  H. Koch,et al.  The vibrational and temperature dependence of the indirect nuclear spin–spin coupling constants of the oxonium (H3O+) and hydroxyl (OH−) ions , 1998 .

[27]  D. Parker.  NMR Determination of Enantiomeric Purity , 1991 .

[28]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[29]  Peer Fischer,et al.  Direct chiral discrimination in NMR spectroscopy , 2006 .

[30]  F. Jensen.  The Basis Set Convergence of Spin-Spin Coupling Constants Calculated by Density Functional Methods. , 2006, Journal of chemical theory and computation.

[31]  S. Kirpekar,et al.  Erratum: “Nuclear spin–spin coupling in the acetylene isotopomers calculated from ab initio correlated surfaces for 1J(C, H), 1J(C, C), 2J(C, H), and 3J(H, H)” [J. Chem. Phys. 112, 3735 (2000)] , 2001 .

[32]  F. Jensen,et al.  Optimization of augmentation functions for correlated calculations of spin-spin coupling constants and related properties. , 2008, The Journal of chemical physics.

[33]  W. T. Raynes,et al.  Nuclear site symmetry and nuclear magnetic shielding in a uniform electric field , 1979 .

[34]  A. Barra,et al.  NMR and parity nonconservation. Experimental requirements to observe a difference between enantiomer signals. , 2001, Chirality.

[35]  David J. Tozer,et al.  Hybrid exchange-correlation functional determined from thermochemical data and ab initio potentials , 2001 .

[36]  P. Provasi,et al.  The effect of lone pairs and electronegativity on the indirect nuclear spin–spin coupling constants in CH2X (X=CH2, NH, O, S): Ab initio calculations using optimized contracted basis sets , 2001 .

[37]  K. Ruud,et al.  COTTON-MOUTON EFFECT AND SHIELDING POLARIZABILITIES OF ETHYLENE: AN MCSCF STUDY , 1997 .

[38]  J. Courtieu,et al.  ENANTIOMERIC ANALYSIS IN A POLYPEPTIDE LYOTROPIC LIQUID CRYSTAL BY DEUTERIUM NMR , 1995 .

[39]  J. Snyder,et al.  Substituent Effects on Scalar 2J(19F,19F) and 3J(19F,19F) NMR Couplings: A Comparison of SOPPA and DFT Methods , 2003 .

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

[41]  S. Sauer,et al.  The calculation and analysis of isotope effects on the nuclear spinspin coupling constants of methane at various temperatures , 1997 .

[42]  R. Nicholls,et al.  Nuclear spin-spin coupling in silane and its isotopomers: Ab initio calculation and experimental investigation , 2001 .

[43]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[44]  J. Elguero,et al.  Systematic Comparison of Second-Order Polarization Propagator Approximation (SOPPA) and Equation-of-Motion Coupled Cluster Singles and Doubles (EOM-CCSD) Spin-Spin Coupling Constants for Molecules with C, N, and O Double and Triple Bonds and Selected F-Substituted Derivatives. , 2009, Journal of chemical theory and computation.

[45]  Jacob Kongsted,et al.  The coupling constant polarizability and hyperpolarizabilty of 1J(NH) in N‐methylacetamide, and its application for the multipole spin–spin coupling constant polarizability/reaction field approach to solvation , 2011, J. Comput. Chem..

[46]  R. Berger,et al.  Ab initio calculation of parity-violating chemical shifts in NMR spectra of chiral molecules. , 2003, Chemphyschem : a European journal of chemical physics and physical chemistry.

[47]  Antonio Rizzo,et al.  Electric field dependence of magnetic properties: Multiconfigurational self‐consistent field calculations of hypermagnetizabilities and nuclear shielding polarizabilities of N2, C2H2, HCN, and H2O , 1995 .

[48]  J. Kongsted,et al.  Benchmarking the multipole shielding polarizability/reaction field approach to solvation against QM/MM: applications to the shielding constants of N-methylacetamide. , 2011, The Journal of chemical physics.

[49]  N. Ramsey.  Electron Coupled Interactions between Nuclear Spins in Molecules , 1953 .

[50]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[51]  A. Buckingham,et al.  The ab initio computation of some magnetic properties and their variation with an electric field , 1976 .

[52]  W. T. Raynes.  Effects of Isotopic Substitution and Temperature on Nuclear Magnetic Shielding , 1993 .

[53]  A. J. Sadlej,et al.  Accurate coupled Hartree-Fock calculations of the electric-field dependence of the proton magnetic shielding in the hydrogen molecule , 1978 .

[54]  S. Kirpekar,et al.  Nuclear spin–spin coupling in the acetylene isotopomers calculated from ab initio correlated surfaces for 1J(C, H), 1J(C, C), 2J(C, H), and 3J(H, H) , 2000 .

[55]  A. D. Buckingham,et al.  Chirality in NMR spectroscopy , 2004 .

[56]  S. Sauer,et al.  Calculated spin± spin coupling surfaces in the water molecule; prediction and analysis of J(O,H), J(O, D) and J(H, D) in water isotopomers , 1998 .

[57]  J. Kongsted,et al.  Benchmarking NMR indirect nuclear spin-spin coupling constants: SOPPA, SOPPA(CC2), and SOPPA(CCSD) versus CCSD. , 2010, The Journal of chemical physics.

[58]  T. Enevoldsen,et al.  Correlated calculations of indirect nuclear spin-spin coupling constants using second-order polarization propagator approximations: SOPPA and SOPPA(CCSD) , 1998 .

[59]  P. Jensen,et al.  Thermal averaging of the indirect nuclear spin-spin coupling constants of ammonia: the importance of the large amplitude inversion mode. , 2010, The Journal of chemical physics.

[60]  Stefano Pelloni,et al.  Chiral discrimination via nuclear magnetic shielding polarisabilities from NMR spectroscopy: Theoretical study of (Ra)‐1,3‐dimethylallene, (2R)‐2‐methyloxirane, and (2R)‐N‐methyloxaziridine , 2007, J. Comput. Chem..

[61]  S. Sauer.  Second-order polarization propagator approximation with coupled-cluster singles and doubles amplitudes - SOPPA(CCSD): the polarizability and hyperpolarizability of , 1997 .

[62]  D. M. Bishop,et al.  Electron-correlated calculations of the nuclear-shielding polarizability and magnetizability polarizability of H2, N2, HF, and CO , 1996 .

[63]  Ove Christiansen,et al.  Atomic integral driven second order polarization propagator calculations of the excitation spectra of naphthalene and anthracene , 2000 .

[64]  A. Soncini,et al.  Parity-violating contributions to nuclear magnetic shielding , 2003 .

[65]  M. Caputo,et al.  Shielding polarizabilities via continuous transformation of the origin of the current density in the set of small molecules: H2O2,F2,H2C2,H2CO,NH3, HCN, and HNC , 2000 .

[66]  P. Provasi,et al.  On the Angular Dependence of the Vicinal Fluorine-Fluorine Coupling Constant in 1,2-Difluoroethane:  Deviation from a Karplus-like Shape. , 2006, Journal of chemical theory and computation.

[67]  D. M. Bishop,et al.  Calculations of magnetic properties , 1993 .