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| - NMR Solvent Shifts of Acetonitrile from Frozen Density Embedding Calculations
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| - We present a density functional theory (DFT) study of solvent effects on nuclear magnetic shielding parameters.As a test example we have focused on the sensitive nitrogen shift of acetonitrile immersed in a selected setof solvents, namely water, chloroform, and cyclohexane. To include the effect of the solvent environment inan accurate and efficient manner, we employed the frozen-density embedding (FDE) scheme. We have includedup to 500 solvent molecules in the NMR computations and obtained the cluster geometries from a large setof conformations generated with molecular dynamics. For small solute−solvent clusters comparison of theFDE results with conventional supermolecular DFT calculations shows close agreement. For the large solute−solvent clusters the solvent shift values are compared with experimental data and with values obtained usingcontinuum solvent models. For the water → cyclohexane shift the obtained value is in very good agreementwith experiments. For the water → chloroform NMR solvent shift the classical force field used in the moleculardynamics simulations is found to introduce an error. This error can be largely avoided by using geometriestaken from Car−Parrinello molecular dynamics simulations.
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