title: Potential energy surface of fluoroxene: experiment and theory.
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 CH2=CH-O-CH2- and trans for the =CH-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 (13)C and (18)O 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.
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080, Bilbao, Spain. emiliojose.cocinero@ehu.es.
authors.forename: Iciar
authors.initials: I
authors.lastname: Uriarte
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080, Bilbao, Spain. emiliojose.cocinero@ehu.es.
authors.forename: Patricia
authors.initials: P
authors.lastname: Écija
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080, Bilbao, Spain. emiliojose.cocinero@ehu.es and Department of Chemistry, University of Bologna, Via Selmi 2, I-40126, Bologna, Italy.
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Spada
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080, Bilbao, Spain. emiliojose.cocinero@ehu.es.
authors.forename: Eneko
authors.initials: E
authors.lastname: Zabalza
authors.affiliation: Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47011, Valladolid, Spain.
authors.forename: Alberto
authors.initials: A
authors.lastname: Lesarri
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080, Bilbao, Spain. emiliojose.cocinero@ehu.es.
authors.forename: Francisco J
authors.initials: FJ
authors.lastname: Basterretxea
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080, Bilbao, Spain. emiliojose.cocinero@ehu.es.
authors.forename: José A
authors.initials: JA
authors.lastname: Fernández
authors.affiliation: Department of Chemistry, University of Bologna, Via Selmi 2, I-40126, Bologna, Italy.
authors.forename: Walther
authors.initials: W
authors.lastname: Caminati
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080, Bilbao, Spain. emiliojose.cocinero@ehu.es.
authors.forename: Emilio J
authors.initials: EJ
authors.lastname: Cocinero