Varying Projection Quality of Good Local Electric Field Gradients of Monochlorobenzaldehydes.

Abstract

Rotational spectroscopy is an excellent tool for structure determination, which can provide additional insights into local electronic structure by investigating the hyperfine pattern due to nuclear quadrupole coupling. Jet-cooled molecules are good experimental benchmark targets for electronic structure calculations, as they are free of environmental effects. We report the rotational spectra of 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, and 4-chlorobenzaldehyde, including a complete experimental description of the nuclear quadrupole coupling constants, which were previously not experimentally determined. We identified two conformers for 3-chlorobenzaldehyde and one conformer each for 2-chlorobenzaldehyde and 4-chlorobenzaldehyde. Rigorous structure fitting of 4-chlorobenzaldehyde was performed to determine bond lengths for r₀, r_s, r_e^se, and r_m⁽¹⁾ structures. Comparing experimental nuclear quadrupole coupling constants to computational results showed agreement in the nuclear axis system, but the accuracy of the projection into the principal axis system decreases in near-oblate 2-chlorobenzaldehyde. The experimental angle Θ_az = 19.16° between the principal a-axis and nuclear z-axis is larger than predicted by multiple computational methods by ≥4°. It is attributed to the high sensitivity of 2-chlorobenzaldehyde to low-energy vibrational contributions.