Conformational study and reassessment of the vibrational assignments for Norspermidine

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 157; pp. 227 - 237
• Main Authors: Silva, T.M., Fiuza, S.M., Marques, M.P.M., Batista de Carvalho, L.A.E., Amado, A.M.
• Format: Journal Article
• Language: English
• Published: England Elsevier B.V 15.03.2016
• Subjects: Conformational preferences; Dielectric constant effect; Norspermidine; Quantum chemical calculations; Vibrational spectroscopy; Dielectric constant effect; Conformational preferences; Quantum chemical calculations; Norspermidine; Vibrational spectroscopy
• ISSN: 1386-1425; 1873-3557
• DOI: 10.1016/j.saa.2016.01.003

The present study presents and discusses the conformational preferences of Norspermidine (NSpd). The effects of varying the dielectric constant on the conformational preferences are discussed, with a view to infer which conformation will correspond to the most stable in the pure condensed liquid phase. Within the same context, a set of NSpd-NH3 molecular adducts were simulated in order to determine the relevance of intermolecular hydrogen bonding on the overall stability and relative positioning of the respective vibrational frequencies. The calculations presently performed allowed a reassessment of the vibrational assignments for NSpd. A full assignment of the NSpd vibrational spectra is presented, with special emphasis being given to the vibrational modes that proved to be most affected by hydrogen bonding. The various inconsistencies of a prior study found in the literature were identified and rectified. An accurate prediction of the vibrational frequencies requires at the outset a correct description of the molecular entity being studied. An incorrect description of the molecular structure and/or electronic distribution will lead to erroneous forecasts of the vibrational frequencies, culminating in inaccurate assignments. [Display omitted]