<p>In this paper, we investigated the non-coincidence effect (NCE), a spectroscopic manifestation of the intermolecular coupling in acetate esters. The isotropic and anisotropic Raman peak frequencies of the C = O stretching mode of ethyl, butyl, and amyl acetates have been discussed in the non-polar solvent carbon tetrachloride using different methods. It was predicted that dipolar forces play a dominant role in the pure state of the studied liquids, as a positive NCE occurred in their C = O stretching mode. The NCE of all selected liquids was determined for solvent and compared with the theoretical Onsager-Fröhlich dielectric continuum model. This theoretical model indicated that intermolecular processes in liquids depend on microscopic parameters such as molecular structure, intermolecular forces, and molecular orientation. Density functional theory calculations and the polarizable continuum model were used to investigate the vibration wavenumber of ethyl, butyl, and amyl acetate dimers at the B3LYP/6–311 + + G(d,p) levels based. Topological analyses, such as non-covalent interaction and reduced density gradient were used to better understand the nature and strength of intermolecular interactions in these dimers. The Mulliken charge distribution and molecular electrostatic potential surface analysis were performed to better understand charge transfer, displacements, and other molecular properties.</p> Graphical Abstract <p></p>