Peculiarities of the SEHRS spectrum of 4,4′-bipyridine molecule

Resumo

The SEHRS spectrum of 4,4′-bipyridine is analyzed on the base of the Dipole-Quadrupole theory. It is demonstrated that there appear strong lines caused by vibrations transforming after the unit irreducible representation of the D₂ symmetry group, which is most probably describes the symmetry properties of the molecule. These lines are nearly forbidden for the molecule, adsorbed on rough metal surfaces. Appearance of these lines is associated with a strong quadrupole light–molecule interaction, which exists in this system. In addition, there are lines caused by contributions from both the vibrations transforming after the unit irreducible representation A and the representation B₁, which describes transformational properties of the d_z component of the dipole moment, which is perpendicular to the surface. This result is associated with the specific geometry of the molecule, when the indicated vibrations can be nearly degenerate and cannot be resolved by the SEHRS spectra analysis. Analysis of the SEHRS spectra for the possible geometry of the molecule with the D_2h symmetry group leads to similar results. This issue is in a full coincidence with the results of the SEHRS Dipole-Quadrupole theory.