Naslov
Infrared Spectroscopy of the Intramolecular Hydrogen Bond in Acetylacetone: A Computational Approach

Autori
Matanović, Ivana ; Došlić, Nađa

Izvornik
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory (1089-5639) 109 (2005); 4185-4194

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
vodikova veza; acetilaceton; teorijska infracrvena spektroskopija
(hydrogen bond; acetylacetone; computational infrared spectroscopy)

Sažetak
The intramolecular hydrogen bond in the enol-acethylacetone (ACAC) is investigated by performing reduced-dimensional quantum calculations. In order to analyze the shared proton vibrations two sets of coordinates were employed: normal mode coordinates describing the motion in vicinity of the most stable configuration, and internal coordinates accounting for the double minimum proton motion. It is proved that the extreme broadness of the OH-stretch band in ACAC is a consequence of the coexistence of two enol-ACAC structures: the global minimum and the transition state for rotation of the distal methyl group. Further, a ground state tunneling splitting of 116 cm-1 is found, and it is shown that the inclusion of the kinematic coupling is mandatory when treating large-amplitude proton motion. In the OH-stretch direction a splitting of 853 cm-1 was predicted.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA