Equilibrium conformation of dimethylaminodichlorophosphine molecule: the use of the results of quantum-chemical calculations and spectroscopic measurements in the analysis of gas-phase electron diffraction data

Abstract

Geometric parameters and force fields of two stable isomers of dimethylaminodichlorophosphine molecule, a gauche-conformer with C1 symmetry (A) and anti-conformer with C s symmetry (D), resulting from internal rotation about the P—N bond, were calculated in the RHF/6-31G* approximation. Using the scaled quantum-chemical force field for the most stable conformer A, the first reliable interpretation of the vibrational spectra of the light and perdeuterated isotopomers of dimethylaminodichlorophosphine was obtained. The root-mean-square vibrational amplitudes, harmonic and anharmonic vibrational corrections, and centrifugal distortion corrections were also calculated. Structural analysis of electron diffraction data was performed with consideration of nonlinear kinematic effects at the first-order level of perturbation theory. The experimental values of the equilibrium geometric parameters were estimated. The results obtained suggest a nonplanar equilibrium configuration of the amino group in the dimethylaminodichlorophosphine molecule.