Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 26463-26470 |
| Seitenumfang | 8 |
| Fachzeitschrift | Physical Chemistry Chemical Physics |
| Jahrgang | 17 |
| Ausgabenummer | 39 |
| Publikationsstatus | Veröffentlicht - 8 Sept. 2015 |
Abstract
Pure six-fold symmetry (V6) internal rotation poses significant challenges to experimental and theoretical determination, as the very low torsional barriers result in huge tunneling splittings difficult to identify and to model. Here we resolved the methyl group internal rotation dynamics of 2,6- and 3,5-difluorotoluene using a newly developed computer code especially adapted to V6 problems. The jet-cooled rotational spectra of the title molecules in the 5-25 GHz region revealed internal rotation tunneling doublings of up to 3.6 GHz, which translated in methyl group potential barriers of V6 = 0.14872(24) and 0.0856(10) kJ mol-1, respectively, in the vibrational ground-state. Additional information on Stark effects and carbon isotopic species in natural abundance provided structural data and the electric dipole moments for both molecules. Ab initio calculations at the MP2 level do not reproduce the tiny torsional barriers, calling for experiments on other systems and additional theoretical models.
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in: Physical Chemistry Chemical Physics, Jahrgang 17, Nr. 39, 08.09.2015, S. 26463-26470.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Six-fold-symmetry internal rotation in toluenes
T2 - the low barrier challenge of 2,6- and 3,5-difluorotoluene
AU - Rajappan Nair, K. P.
AU - Jahn, Michaela K.
AU - Lesarri, Alberto
AU - Ilyushin, Vadim V.
AU - Grabow, Jens Uwe
N1 - Publisher Copyright: This journal is © the Owner Societies.
PY - 2015/9/8
Y1 - 2015/9/8
N2 - Pure six-fold symmetry (V6) internal rotation poses significant challenges to experimental and theoretical determination, as the very low torsional barriers result in huge tunneling splittings difficult to identify and to model. Here we resolved the methyl group internal rotation dynamics of 2,6- and 3,5-difluorotoluene using a newly developed computer code especially adapted to V6 problems. The jet-cooled rotational spectra of the title molecules in the 5-25 GHz region revealed internal rotation tunneling doublings of up to 3.6 GHz, which translated in methyl group potential barriers of V6 = 0.14872(24) and 0.0856(10) kJ mol-1, respectively, in the vibrational ground-state. Additional information on Stark effects and carbon isotopic species in natural abundance provided structural data and the electric dipole moments for both molecules. Ab initio calculations at the MP2 level do not reproduce the tiny torsional barriers, calling for experiments on other systems and additional theoretical models.
AB - Pure six-fold symmetry (V6) internal rotation poses significant challenges to experimental and theoretical determination, as the very low torsional barriers result in huge tunneling splittings difficult to identify and to model. Here we resolved the methyl group internal rotation dynamics of 2,6- and 3,5-difluorotoluene using a newly developed computer code especially adapted to V6 problems. The jet-cooled rotational spectra of the title molecules in the 5-25 GHz region revealed internal rotation tunneling doublings of up to 3.6 GHz, which translated in methyl group potential barriers of V6 = 0.14872(24) and 0.0856(10) kJ mol-1, respectively, in the vibrational ground-state. Additional information on Stark effects and carbon isotopic species in natural abundance provided structural data and the electric dipole moments for both molecules. Ab initio calculations at the MP2 level do not reproduce the tiny torsional barriers, calling for experiments on other systems and additional theoretical models.
UR - http://www.scopus.com/inward/record.url?scp=84942778122&partnerID=8YFLogxK
U2 - 10.1039/c5cp03751d
DO - 10.1039/c5cp03751d
M3 - Article
AN - SCOPUS:84942778122
VL - 17
SP - 26463
EP - 26470
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 39
ER -