RT info:eu-repo/semantics/article
T1 The effect of microsolvation on the structure, nuclear quadrupole coupling, and internal rotation: The methyl carbamate⋯(H2O)1–3 complexes
A1 Pinacho Morante, Pablo
A1 López Alonso, Juan Carlos
A1 Kisiel, Zbigniew
A1 Blanco Rodríguez, Susana
AB Microsolvation of the carbamate moiety delivers precise information on complexation effects on the N–C=O backbone and is of relevance to the peptide bond functionality. In this context, the mono-, di-, and trihydrated complexes of methyl carbamate have been studied in molecular expansion by high-resolution microwave spectroscopy, using chirped-pulse and Fabry–Perot resonator Fourier transform microwave instruments covering the frequency range from 2 to 18 GHz. From the rotational constants of the parent and the 18Ow substituted monoisotopologues, accurate values have been derived for the geometries of the hydrogen bond interactions. The nuclear quadrupole coupling constant χcc of the nitrogen nucleus provides a direct measure of complexation changes and decreases with the degree of hydration, whereas the hindered internal rotation barrier increases slightly with microsolvation. Both tendencies could have a common origin in the π-cooperative inductive effects as the microsolvation series progresses. All transitions are split by the internal rotation of the methyl top and the nuclear quadrupole coupling, and in the largest cluster, they are additionally split by an inversion motion.
SN 0021-9606
YR 2024
FD 2024-04
LK https://uvadoc.uva.es/handle/10324/74224
UL https://uvadoc.uva.es/handle/10324/74224
LA eng
NO The Journal of Chemical Physics, Abril 2024, Vol. 160, n. 16, p. 164315
NO Producción Científica
DS UVaDOC
RD 04-abr-2025