Accurate calculation of electric field gradients (EFGs) in molecular crystals, despite big advances in ab initio techniques, is still a challenge. Here, we present a new approach to calculate the EFGs in molecular crystals by employing the many-body expansion (MBE) technique with electrostatic embedding. This allows for (i) a reduction in the computational cost or an alternative increase in the level of theory (we use the MP2/6-311++G) and (ii) the ability to monitor EFG convergence by progressively adding more surrounding molecules and/or adding higher many-body interactions. We focus on the N-14 EFG and study four (model) compounds in more detail: solid nitrogen, ethylamine, methylamine, and ammonia. Solid nitrogen is rather insensitive to neighbors; for ethylamine and methylamine, the 3-body interactions are found sufficient for a converged EFG, whereas for ammonia, even the inclusion of 5-body interactions is insufficient although convergence is anticipated. We then validate our technique by comparing the experimental and ab initio(14)N EFGs for 116 organic compounds utilizing their known crystal structures and published EFG. Overall, we find a very good agreement, with a small EFG rms error, which is probably due to other sources, rather than the MBE approximation.
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