Combined FTIR/Raman spectroscopic studies and ab initio electronic structure calculations of Dithiothreitol

A total of seven minimum energy geometries were obtained on exploring the conformational landscape of dithiothreitol (DTT) by varying the prominent dihedral angles in the molecule through a relaxed scan with a step size of 5° at B3LYP/cc-pVTZ with further geometry optimization at CCSD/cc-pVDZ level of theory. Single point energies were calculated for all the conformers at CCSD(T)/CBS limit with cc-pVNZ (N = T, Q) level of theory and revealed the similar energy pattern. The two conformers, namely G'TG'1 and G'TT, were found iso-energic even though they differed in their structure significantly and were of the lowest energy compared to others. Energies corresponding to the cyclic as well as other configurational counterpart of the global minimum were found much higher in energy compared to the global minimum structure. Intramolecular sulfur centered hydrogen bond was seen to stabilize the global minimum structure of DTT as revealed by AIM, NBO, FMO and ESP charge analysis. Computed NMR of DTT matched well with the experimental data gleaned from the literature. Vibrational spectra (Raman and IR) were measured and compared with computed normal modes of DTT, which were found in good agreement.