Theoretical calculations and preliminary measurements of vibrational Raman optical activity (ROA) spectra of different species of amphetamine (amphetamine and amphetamine-H+) are reported for the first time. The quantum chemical calculations were carried out as hybrid ab initio DFT-molecular orbital calculations by use of the Gaussian 03W pro- gram, based on complete geometry minimizations of the conformational energy of the S-(+)-amphetamine molecule, the S-(+)-amphetamine-H+ ion, and the R-(–)-amphetamine molecule. Following this, harmonic frequency calculations have been made, providing information about the cation vibrational bands, expected in salts of single anions (chlorides) as well as in salts of anions with internal bonds (sulfates, hydrogen phosphates, etc.). It shows that the kind of anion should be given better attention, as so far it has often not been the case, when the spectra are employed for identification purposes. The DFT calculations show that the most stable conformations are those allowing for close contact between the aromatic ring and the amine hydrogen atoms. The internal rotational barrier within the same amphetamine enanti- omer has a considerable influence on the Raman and ROA spectra. As predicted the experimental ROA spectra were found to depend on the chirality. Two street samples, provided by the London Police, were also measured and compared to the calculated ROA spectra. The street samples were found to contain different enantiomers of the protonated am- phetamine-H+ sulfate. According to the present study the AMPH+ ion in aqueous sulfate solution seems to adopt a con- formation in which the phenyl and ammonium groups are in transpositions, similar to what has been found in the solid state.
- Molecular orbital