The potential energy surface (PES) of the general anesthetic fluoroxene (2,2,2-trifluoroethyl vinyl ether) was probed in a supersonic jet expansion using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy and theoretical calculations. The PES is dominated by a single conformation, as other stable minima are shown to kinetically relax in the expansion to the global minimum. Consistently, the rotational spectrum reveals a single conformation. Fluoroxene adopts a CS heavy-atom planar skeleton structure in the gas phase, with a cis–trans conformation (cis for the CH2QCH–O–CH2– and trans for theQCH–O–CH2–CF3 part). The sensitivity of a recently-built CP-FTMW spectrometer at the UPV/EHU is demonstrated by the detection of five isotopologues of fluoroxene in natural abundance, corresponding to the 13C and 18O monosubstituted species. The rS and r0 structures were determined and are in good agreement with theoretical predictions using the MP2, B3LYP and M06-2X methods.
Potential energy surface of fluoroxene: experiment and theory / Uriarte, Iciar; Écija, Patricia; Spada, Lorenzo; Zabalza, Eneko; Lesarri, Alberto; Basterretxea, Francisco J.; Fernández, José A.; Caminati, Walther; Cocinero, Emilio J.. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - STAMPA. - 18:5(2016), pp. 3966-3974. [10.1039/C5CP06522D]
Potential energy surface of fluoroxene: experiment and theory
SPADA, LORENZO;CAMINATI, WALTHER;
2016
Abstract
The potential energy surface (PES) of the general anesthetic fluoroxene (2,2,2-trifluoroethyl vinyl ether) was probed in a supersonic jet expansion using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy and theoretical calculations. The PES is dominated by a single conformation, as other stable minima are shown to kinetically relax in the expansion to the global minimum. Consistently, the rotational spectrum reveals a single conformation. Fluoroxene adopts a CS heavy-atom planar skeleton structure in the gas phase, with a cis–trans conformation (cis for the CH2QCH–O–CH2– and trans for theQCH–O–CH2–CF3 part). The sensitivity of a recently-built CP-FTMW spectrometer at the UPV/EHU is demonstrated by the detection of five isotopologues of fluoroxene in natural abundance, corresponding to the 13C and 18O monosubstituted species. The rS and r0 structures were determined and are in good agreement with theoretical predictions using the MP2, B3LYP and M06-2X methods.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
