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| Author(s): |
Carlos Roberto Martins da Cunha
Total Authors: 1
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| Document type: | Doctoral Thesis |
| Press: | São Paulo. |
| Institution: | Universidade de São Paulo (USP). Instituto de Física (IF/SBI) |
| Defense date: | 1997-10-30 |
| Examining board members: |
Sylvio Roberto Accioly Canuto;
Luiz Marco Brescansin;
Marcos Antônio de Castro;
Adalberto Fazzio;
Mario Jose de Oliveira
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| Advisor: | Sylvio Roberto Accioly Canuto |
| Abstract | |
The intermolecular interaction betwen N2 C5H5 , He C5H5 and Ne C5H5 is analyzed using second-order many-body perturbation theory. For these systems the interaction is dominated by the van der Waals contribution of the London dispersion force. For N2 C5H5 it is found that the system is stable by rv400 cm-1 at an intermolecular distance of 3,4 A. Analysis of the electrostatic quadrupole-quadrupole interaction shows that the system is stabilized when N2 lies parallel to the C5H5 plane and is destabilized when N2 lies perpendicular to the C5H5 plane. Therefore, although the dispersion force is the major contributor to the stabilization it is the quadrupole-quadrupole interaction that is held responsible for the favourable structure. In the case of both He C5H5 and Ne C5H5 there is no direct electrostatic interaction as the permanent moments of He and Ne are zero. For the He C5 H5 it is found a very small binding energy, if any. As for the Ne C5H5 we find a binding energy of around 100 cm-1. This different behavior for He and Ne is analyzed using the calculated values for the dipole polarizabilities. The influence of the different geometries for C5H5 (C 2v or D5h) as well as the so-called basis set superposition error are analyzed. For isolated C5H5 high-order calculations show that the 2B2 ground state for symmetry C2v lies around 0,2 eV below the 2E ground state for symmetry D5h. This energy lowering comes from the expected Jahn-Teller distortion. (AU) | |