Comment on "The Nature of Chalcogen-Bonding-Type Tellurium-Nitrogen Interactions": Fixing the Description of Finite-Temperature Effects Restores the Agreement Between Experiment and Theory.

ABSTRACT: Mitzel and co-workers recently presented an intriguing molecule displaying a tellurium-nitrogen interaction. Structural data obtained in the solid and in gas phase indicated a large increase of the Te-N equilibrium distance r_e from 2.64 to 2.92 Å, respectively. Although some DFT calculations appear to support the large r_e in gas phase, we argue that the lions share of the increase is due to an incomplete description of finite-temperature effects in the back-corrected experimental data. This hypothesis is based on high-level coupled-cluster (CC) and periodic DFT calculations, which consistently point towards a much smaller r_e in the isolated molecule. Further support comes through MD simulations with a tuned GFN2-xTB Hamiltonian: Calibrated against a CC reference, these show a six-times larger influence of temperature than with the originally used GFN1-xTB. Taking this into account, the back-corrected r_e in gas phase becomes 2.67±0.08 Å, in good agreement with high-level CC theory and most DFT methods.

SUBMITTER: Mewes JM 

PROVIDER: S-EPMC8252449 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature