Calculated nuclear shielding surfaces in the water molecule; prediction and analysis of σ(O), σ(H) and σ(D) in water isotopomers

Wigglesworth, Richard D.; Raynes, W.T.; Sauer, Stephan P. A.; Oddershede, Jens

doi:10.1080/00268979909483103

Cited by 30 publications

(20 citation statements)

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“…48,60-62 As expected, our zero-point vibrational corrections are in good agreement with the CASSCF results of Wigglesworth et al 57 since we use the same wave function, the differences being due mainly to the difference in force field and perturbation expansion of the vibrational wave function and to some extent also because of the different isotopic species investigated. It is also worth noticing that our CASSCF wave function is much more successful in recovering the correlation effects on the ZPVCs to the nuclear shieldings than was the case for the ZPVC to the rotational g tensor.…”

Section: Scfsupporting

confidence: 83%

“…Our results cannot therefore be directly compared to experiment, nor to the other theoretical studies which both studied the isotopic species H 2 17 O. 3,57 However, these differences should, considering the relatively minor difference in the total mass of the system, be rather small.…”

Section: Scfmentioning

confidence: 80%

“…It appears that only a limited number of correlated studies have been undertaken on vibrational corrections to the molecular properties of the water molecule, and our comparison will therefore be restricted to a comparison with the MP2 results of Russell and Spackman for the electric properties, 27 and results previously obtained by one of us using larger multiconfigurational SCF expansions than that employed here for the magnetic properties 3,17 and finally a CASSCF study of the nuclear shieldings by Wigglesworth et al 57 using the same active space we use here, but employing an experimental force field. All these result are collected in Table VI.…”

Section: B Watermentioning

confidence: 99%

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An efficient approach for calculating vibrational wave functions and zero-point vibrational corrections to molecular properties of polyatomic molecules

Ruud

Åstrand

Taylor

2000

The Journal of Chemical Physics

214

172

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Articles you may be interested inA virtual vibrational self-consistent-field method for efficient calculation of molecular vibrational partition functions and thermal effects on molecular properties Density functional self-consistent quantum mechanics/molecular mechanics theory for linear and nonlinear molecular properties: Applications to solvated water and formaldehyde Analytic calculation of first-order molecular properties at the explicitly correlated second-order Møller-Plesset level: Basis-set limits for the molecular quadrupole moments of BH and HFWe have recently presented a formalism for calculating zero-point vibrational corrections to molecular properties of polyatomic molecules in which the contribution to the zero-point vibrational correction from the anharmonicity of the potential is included in the calculations by performing a perturbation expansion of the vibrational wave function around an effective geometry. In this paper we describe an implementation of this approach, focusing on computational aspects such as the definition of normal coordinates at a nonequilibrium geometry and the use of the Eckart frame in order to obtain accurate nonisotropic molecular properties. The formalism allows for a black-box evaluation of zero-point vibrational corrections, completed in two successive steps, requiring a total of two molecular Hessians, 6K -11 molecular gradients, and 6K -11 property evaluations, K being the number of atoms. We apply the approach to the study of a number of electric and magnetic properties-the dipole and quadrupole moments, the static and frequency-dependent polarizability, the magnetizability, the rotational g tensor and the nuclear shieldings-of the molecules hydrogen fluoride, water, ammonia, and methane. Particular attention is paid to the importance of electron correlation and of the importance of the zero-point vibrational corrections for obtaining accurate estimates of molecular properties for a direct comparison with experiment.

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Section: Scfsupporting

confidence: 83%

Section: Scfmentioning

confidence: 80%

Section: B Watermentioning

confidence: 99%

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An efficient approach for calculating vibrational wave functions and zero-point vibrational corrections to molecular properties of polyatomic molecules

Ruud

Åstrand

Taylor

2000

The Journal of Chemical Physics

214

172

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“…It is now a routine procedure to include the effects of electron correlation and correlated shielding surfaces fully to second order are presently available for the nuclei in water, [5][6][7] ammonia, 5,8 phosphine, 5 and the carbon nucleus of methane. 5 Recently, noncorrelated shielding surface coefficients have been obtained for the nuclei in OCS, 9 CSe 2 , 10 and the methyl halide molecules CH 3 X͑XϭF, Cl, Br͒.…”

Section: Introductionmentioning

confidence: 99%

Nuclear magnetic shielding in the acetylene isotopomers calculated from correlated shielding surfaces

Wigglesworth

Raynes

Kirpekar

et al. 2000

The Journal of Chemical Physics

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Articles you may be interested inCurrent density maps, magnetizability, and nuclear magnetic shielding tensors of bis-heteropentalenes. I. Dihydro-pyrrolo-pyrrole isomers Natural chemical shielding analysis of nuclear magnetic resonance shielding tensors from gauge-including atomic orbital calculations Ab initio, symmetry-coordinate and internal valence coordinate carbon and hydrogen nuclear shielding surfaces for the acetylene molecule are presented. Calculations were performed at the correlated level of theory using gauge-including atomic orbitals and a large basis set. The shielding was calculated at equilibrium and at 34 distinct geometries corresponding to 53 distinct sites for each nucleus. The results were fitted to fourth order in Taylor series expansions and are presented to second order in the coordinates. The carbon-13 shielding is sensitive to all geometrical parameters and displays some unexpected features; most significantly, the shielding at a carbon nucleus ͑C 1 , say͒ is six times more sensitive to change of the C 1 C 2 H 2 angle than it is to change of the H 1 C 1 C 2 angle. In addition, for small changes, ͑C 1 ͒ is more sensitive to the C 2 H 2 bond length than it is to the C 1 H 1 bond length. These, and other, examples of ''unexpected differential sensitivity'' are discussed. The proton shielding surface is much more as expected with ͑H 1 ͒ being most sensitive to the C 1 H 1 bond length, less so to the CC bond length and hardly at all to the C 2 H 2 bond length. The surfaces have been averaged over a very accurate force field to give values of ͑C͒, ͑H͒, and ͑D͒ for the ten isotopomers containing all possible combinations of 12 C, 13 C, 1 H, and 2 H nuclei at 0 K and at a number of selected temperatures in the range accessible to experiment. For the carbon shielding the dominant nuclear motion contribution comes from the bending at ''the other'' carbon atom with the combined stretching contributions being only 20% of those from bending. For the proton shielding it is the stretching of the CH bond containing the proton of interest which provides the major nuclear motion contribution. For ͑C͒ in H 13 C 13 CH at 300 K our best result is 117.59 ppm which is very close to the experimental value of 116.9 ͑Ϯ0.9͒ ppm. For ͑H͒ in H 13 C 13 CH at 300 K we obtain 29.511 ppm which is also in very close agreement with the experimental value of 29.277 ͑Ϯ0.001͒ ppm. Calculated values are also very close to recent, highly accurate carbon and proton isotope shifts in the ten isotopomers; carbon isotope shifts differ by no more than 10% from the measured values and proton isotope shifts are generally in even better agreement than this. The observed anomaly whereby the 13 C isotope shift in H 13 C 12 CD is greater than that in D 13 C 12 CH both with respect to H 13 C 12 CH is explained in terms of the bending contribution at ''the other'' carbon. The observed nonadditivity of deuterium isotope effects on the carbon shielding can be traced to a cross term involving second order bending.

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“…[1,5,8,21 -31] Extrapolation of NMR results obtained with systematically improved basis sets toward the basis set limit, called here the CBS limit approach, could help to discriminate between the accidentally good agreement of theoretical results obtained with Obviously, for a reliable comparison of predicted isotropic shieldings and SSCC values with those from experiment, the zero-point rovibrational corrections (ZPVCs) should be taken into account. [27,28,38,39] Among the several works on the calculations of rovibrational corrections for NMR parameters are those by Casanueva et al, [30] Vaara et al, [40] Wigglesworth et al, [41,42] Ruden et al, [43] and Ruud et al [38,44] Calculation of ZPVCs is a very demanding task computationally. [28,30,34,43,45] Thus, instead of rigorous calculations of rovibrational and thermal corrections, some authors have suggested a more approximate approach by direct transfer of ZPVCs within similar compounds and molecular fragments (see Ruud et al [45] ).…”

Section: Introductionmentioning

confidence: 99%

Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polarization‐consistent basis sets in the Kohn–Sham basis set limit

Kupka

2008

Magnetic Reson in Chemistry

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Density functional theory (DFT) was used to estimate water's isotropic nuclear shieldings and indirect nuclear spin-spin coupling constants (SSCCs) in the Kohn-Sham (KS) complete basis set (CBS) limit. Correlation-consistent cc-pVxZ and cc-pCVxZ (x = D, T, Q, 5, and 6), and their modified versions (ccJ-pVxZ, unc-ccJ-pVxZ, and aug-cc-pVTZ-J) and polarization-consistent pc-n and pcJ-n (n = 0, 1, 2, 3, and 4) basis sets were used, and the results fitted with a simple mathematical formula. The performance of over 20 studied density functionals was assessed from comparison with the experiment. The agreement between the CBS DFT-predicted isotropic shieldings, spin-spin values, and the experimental values was good and similar for the modified correlation-consistent and polarization-consistent basis sets. The BHandH method predicted the most accurate (1)H, (17)O isotropic shieldings and (1)J(OH) coupling constant (deviations from experiment of about -0.2 and -1 ppm and 0.6 Hz, respectively). The performance of BHandH for predicting water isotropic shieldings and (1)J(OH) is similar to the more advanced methods, second-order polarization propagator approximation (SOPPA) and SOPPA(CCSD), in the basis set limit.

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Calculated nuclear shielding surfaces in the water molecule; prediction and analysis of σ(O), σ(H) and σ(D) in water isotopomers

Cited by 30 publications

References 60 publications

An efficient approach for calculating vibrational wave functions and zero-point vibrational corrections to molecular properties of polyatomic molecules

An efficient approach for calculating vibrational wave functions and zero-point vibrational corrections to molecular properties of polyatomic molecules

Nuclear magnetic shielding in the acetylene isotopomers calculated from correlated shielding surfaces

Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polarization‐consistent basis sets in the Kohn–Sham basis set limit

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