The electronic structures of benzene and p-xylene have been investigated by the discrete-variational Hartree-Fock-Slater Xα method. The DVM-Xα scheme employing numerical atomic basis functions permits more accurate solution of the Schrödinger equation than do muffin-tin methods, while requiring less computing resources than other first-principles methods. This enables one to study large molecules and clusters without empirical input. Previous applications of the method using an approximate, spherically averaged potential around each atom have proven inaccurate in studies of several small molecules, notably those with a large percentage of hydrogen atoms. Recent modifications of the method which include a multipolar expansion of the molecular potential have improved the accuracy of one-electron binding energies significantly. These improvements are illustrated by calculations of the ionization energies of benzene and p-xylene; detailed comparisons are made to experimental data and assignments from previous calculations. It appears that the local-density technique is quite good for description of the photoelectron spectra of these molecules.
|Number of pages||3|
|Journal||Journal of Physical Chemistry|
|Publication status||Published - 1984|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry