Reply to a Comment on "The Nature of Chalcogen-Bonding-Type Tellurium-Nitrogen Interactions"

Area of Science:

• Chemical Physics
• Spectroscopy
• Computational Chemistry

Background:

• The study addresses a critique regarding the N⋅⋅⋅Te internuclear distance determined by gas electron diffraction (GED) for (C6F5)Te(CH2)3NMe2.
• The critique questioned the accuracy of the experimental r_e value, proposing alternative computational methods and interpretations.

Discussion:

• The authors demonstrate that the reference calculations cited by the critics are less accurate for both gas and solid phases than claimed.
• Higher-level computational analyses confirm that contributions from open-chain conformers were not significantly underestimated and would negligibly affect the N⋅⋅⋅Te distance.
• Vibrational correction calculations using a suggested H0-tuned GFN method did not substantially alter the r_a - r_e values.

Key Insights:

• Revised calculations using advanced force fields (PBE0-D3BJ/def2-TZVP) yield an r_e(N⋅⋅⋅Te) of 2.852(25) Å, consistent with the original GED measurement of 2.918(31) Å.
• The critics' predicted value of 2.67(8) Å is shown to be inaccurate.
• An improved error estimation accounts for auxiliary calculation inaccuracies, reinforcing the reliability of the experimental findings.

Outlook:

• The observed gas/solid difference for the weak N⋅⋅⋅Te interaction is deemed realistic when compared to similar systems.
• This work highlights the importance of rigorous validation of computational methods against experimental data in structural chemistry.
• Further investigations into weak non-covalent interactions using complementary experimental and computational approaches are warranted.