Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions
- Departament de Química Orgànica, Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martí i Franquès, 1, 08028 Barcelona (Spain)
- Dipartimento di Fisica, Università degli Studi di Trento, 38123 Povo-Trento (Italy)
Collisions between potassium ions and neutral i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH, all in their electronic ground state, have been studied in the 0.10–10.00 eV center of mass (CM) collision energy range, using the radiofrequency-guided ion beam technique. In K{sup +} + i-C{sub 3}H{sub 7}Br collisions KHBr{sup +} formation was observed and quantified, while the analogous KH{sub 2}O{sup +} formation in K{sup +} + i-C{sub 3}H{sub 7}OH was hardly detected. Moreover, formation of the ion-molecule adducts and their decomposition leading to C{sub 3}H{sub 7}{sup +} and either KBr or KOH, respectively, have been observed. For all these processes, absolute cross-sections were measured as a function of the CM collision energy. Ab initio structure calculations at the MP2 level have given information about the potential energy surfaces (PESs) involved. In these, different stationary points have been characterized using the reaction coordinate method, their connectivity being ensured by using the intrinsic-reaction-coordinate method. From the measured excitation function for KHBr{sup +} formation the corresponding thermal rate constant at 303 K has been calculated. The topology of the calculated PESs allows an interpretation of the main features of the reaction dynamics of both systems, and in particular evidence the important role played by the potential energy wells in controlling the reactivity for the different reaction channels.
- OSTI ID:
- 22310751
- Journal Information:
- Journal of Chemical Physics, Vol. 141, Issue 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Kinetics and thermochemistry of R + HBr {r_reversible} RH + Br reactions: Determinations of the heat of formation of C{sub 2}H{sub 5}, i-C{sub 3}H{sub 7}, sec-C{sub 4}H{sub 9}, and t-C{sub 4}H{sub 9}
Mechanistic investigation of carbon-carbon bond formation in the reduction of alkyl halides by organonickel complexes in aqueous solution. [R'X (R' = CH/sub 3/, C/sub 2/H/sub 5/, 1-C /sub 3/H/sub 7/, 2-C/sub 3/H/sub 7/, and PhCH/sub 2/; X = Cl, Br, I) RNi(tmc)/sup +/ (R = C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, and CH/sub 2/-c-C/sub 5/H/sub 9/; tmc = (1R,4R,8S,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)]