Evidence for a blue-shifting intramolecular hydrogen bond in the vibrational overtone spectrum of 1H-nonafluorobutane

Autor:	Brian G. Saar, Geoff P. O’Donoghue, John W. Thoman, Adam H. Steeves
Rok vydání:	2006
Předmět:	Bond length Crystallography Chemistry Hydrogen bond Intramolecular force Overtone General Physics and Astronomy Density functional theory Electronic structure Physical and Theoretical Chemistry Photochemistry Spectroscopy Conformational isomerism
Zdroj:	Chemical Physics Letters. 417:159-163
ISSN:	0009-2614
DOI:	10.1016/j.cplett.2005.09.124
Popis:	We demonstrate that the gauche conformation of 1H-nonafluorobutane contains a blue-shifting intramolecular hydrogen bond by recording its 5th overtone spectrum with cavity ringdown spectroscopy and performing electronic structure calculations. The magnitude of the blue-shift is enhanced in the overtone spectrum as compared to the fundamental. The energy difference between the gauche conformer and the lowest energy zigzag conformer is calculated to be 288 cm−1 using density functional theory and determined to be 280 ± 30 cm−1 using temperature-dependent FTIR measurements. The –H⋯F– bonding interaction in the gauche conformer leads to changes in bond lengths as compared to the non-hydrogen bonded conformers.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::45d856c3e5a3fdf520f6a16862dffb9a https://doi.org/10.1016/j.cplett.2005.09.124 Zobrazit plný text záznamu Full Text from ScienceDirect