Diffraction Measurements and Equilibrium Parameters

Abstract EN

Structural studies are largely performed without taking into account vibrational effects or with incorrectly taking them into account.

The paper presents a first-order perturbation theory analysis of the problem.

It is shown that vibrational effects introduce errors on the order of 0.02 Å or larger (sometimes, up to 0.1-0.2 Å) into the results of diffraction measurements.

Methods for calculating the mean rotational constants, mean-square vibrational amplitudes, vibrational corrections to internuclear distances, and asymmetry parameters are described.

Problems related to low-frequency motions, including torsional motions that transform into free rotation at low excitation levels, are discussed.

The algorithms described are implemented in the program available from the author (free).