A MULTICONFIGURATIONAL LINEAR RESPONSE STUDY OF N2
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abstract
The multiconfigurationai time-dependent Hartree-Fock (MCTDHF) method (which is the correct linear response for a multiconfigurational wavefunction) has been applied in a study of the linear response properties of N2. The excitation energies, transition moments, static and dynamic dipole polarizabilities, magnetic susceptibility and nitrogen atom NMR shielding constant were analyzed. Several CGTO basis sets were used. With the largest CGTO basis set (124 functions) our TDHF results appear to be close to the Hartree-Fock response limits. For most of the low-lying excitation energies the MCTDHF calculation, which takes into account some valence shell correlation effects, yields results significantly improved with respect to TDHF. We present also the results for some higher lying excitations of particular interest for experimentalists, i.e. 1u+ excitations 23-35 eV, the 1u, excitation observed at 23 eV, and a 1g transition observed at 31.4 eV. An analysis of the computed electric and magnetic properties indicates that they are strongly dependent on correlation corrections. The calculations of magnetic properties are the first to explicitly include correlation effects for a system this large. 1989.
