Ab initio study of the biogenic amino acids

Abstract

Ten amino acids have been subjected to the quantum chemical calculations using the ab initio MO-LCAO-SCF calculations. When the geometry optimization started form the X-ray structure confirming the zwitterionic form, the ab initio calculations in vacuo result in the amino acid (canonical) form with the hydrogen atom attached not to the amine but to the carboxylate group. At the optimum geometry, a number of properties were evaluated: dipole moment, dipole polarizability, molecular surface, molecular volume, HOMO, LUMO, ionization energy, and electron affinity using the ΔSCF approach and their values corrected for electron correlation by the 2nd order perturbation theory (MP2). Also, the Mulliken electronegativity and Pearson hardness were evaluated. These properties have been mutually correlated by employing the statistical multivariate methods: the cluster analysis, the probabilistic neural network classifier, the principal component analysis, and the Pearson pair correlation. In addition, the molecular electrostatic potential mapped on the isovalue surface of charge density has been drawn. After the full vibrational analysis, thermodynamic properties at 300 K were evaluated: internal energy, entropy, and the free energy.

Keywords: Ab initio calculations; Amino acids; Molecular properties; Multivariate methods.