Part of the book: Electronic Properties of Carbon Nanotubes
Density functional theory (DFT) was employed to investigate protonation, deuteration, and substitution effects on the vibrational spectra of porphyrin molecules. The results of the calculations were compared with experimental data. The calculations show that meso‐substitutions produced a substantial shift in frequencies when the meso‐carbons within the parent porphine are involved in the vibrational motion of molecules, while protonation of the N atoms leads to a significant blue shift when the H atoms covalent bonded to the N atoms that are substantially involved in the vibrational motion. Deuteration of N atoms at the porphyrin core is found to result not only in a red shift in the frequencies of the corresponding peaks below 1600 cm-1, but also to generate new Raman bands of frequencies in the range of 2565–2595 cm-1, resulting from N‐D bond stretching. Also, the deuteration of O atoms within the sulfonato groups (‐SO3-) results in a new peak at near 2642 cm-1 due to O‐D bond stretching. Calculated IR spectra of the compounds studied here showed similar differences. Finally, we discuss solvent effects on the IR spectrum of TSPP.