Surfaced-enhanced Ramon scattering (SERS) spectra of pyrazine are analyzed on the basis of the properties of the electronic states of the metal-adsorbate surface complex. Ab initio CIS calculations have been carried out for the ${\mathrm{Ag}}_2$ -pyrazine complex, which have enabled us to find two excited singlets, namely ${\mathrm{CT}}_0{;}^1{B}_1$ and ${\mathrm{CT}}_1{;}^1{A}_2,$ with properties quite similar to those of the pyrazine radical anion in its electronic ${}^2{B}_{\text{3u}}$ and ${}^2{A}_u$ states, respectively, and with energies falling in the range of the exciting photons usually employed in Raman spectroscopy. SERS spectra of pyrazine are compatible with a resonance Raman enhancement mechanism involving electronic transitions between the ground state $S_0{;}^1{A}_1$ and both CT levels of the surface complex.

The relevant low-lying singlet and triplet potential energy surfaces in the photolysis of nitromethane have been studied by using the multistate extension of the multiconfigurational second-order perturbation theory in conjunction with large atomic natural orbital-type basis sets. The proposed mechanism for the photolytic decomposition of CH3NO2 provides a consistent and reinterpreted picture of the available experimental results. Two reaction paths are found in the photolysis of nitromethane after excitation at 193 nm: (1) Major Channel, CH3NO2(1A′)+hν(193 nm)→CH3NO2(2A″)→ lim ICCH3NO2(2A′)→CH3(1A1′)+NO2(1 2B1)→ lim −hν′ICCH3(1A1′)+NO2(1 2A1)→ lim 193 nmhνCH3(1A1′)+NO(A 2Σ+)+αO(3P)+βO(1D). (2) Minor Channel, CH3NO2(1A′)+hν(193 nm)→CH3NO2(2A″)→CH3(1A1′)+NO2(1 2A2)→CH3(1A1′)+NO(X 2Π)+αO(3P)+βO(1D), being α and β fractional numbers. No ionic species are found in any dissociation path. Additionally, the respective low-lying Rydberg states of nitromethane and nitrogen dioxide have been studied too.