Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 13775-13778 |
| Seitenumfang | 4 |
| Fachzeitschrift | Journal of Physical Chemistry A |
| Jahrgang | 117 |
| Ausgabenummer | 50 |
| Publikationsstatus | Veröffentlicht - 19 Dez. 2013 |
Abstract
Ab initio calculations of the six-dimensional intermolecular potential have shown the benzene dimer to be an asymmetric top molecule at equilibrium with one benzene moiety forming the "stem" and the other a "tilted cap" in a T-shaped structure. Internal rotation of the cap about its C 6 axis is essentially free; the barriers for cap tilting and for internal rotation of the stem about its C6 axis are hindered by successively higher barriers. In previous work we have validated these theoretical results using Fourier transform microwave spectroscopy in conjunction with dynamics calculations. We have also measured the Stark effect, and despite the fact that the equilibrium structure is that of an asymmetric top, the assigned transitions involving K = 0 exhibit a second-order Stark effect whereas those involving K = 1 exhibit a first-order Stark effect. This is typical for a symmetric-top molecule, but anomalous for an asymmetric-top molecule. We use symmetry arguments to explain how this asymmetric-top molecule can have a first-order Stark effect in certain states that have excitation of cap internal rotation. Cap internal rotation is essentially the twisting of the monomers relative to each other about the intermolecular axis, and such torsional motion occurs in other asymmetric top dimers such as benzene-CO and benzene-H2O. These latter dimers will also have levels that exhibit a first-order Stark effect, which we can explain using our symmetry arguments.
ASJC Scopus Sachgebiete
- Chemie (insg.)
- Physikalische und Theoretische Chemie
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in: Journal of Physical Chemistry A, Jahrgang 117, Nr. 50, 19.12.2013, S. 13775-13778.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Stark effect in the benzene dimer
AU - Schnell, Melanie
AU - Bunker, P. R.
AU - Von Helden, Gert
AU - Grabow, Jens Uwe
AU - Meijer, Gerard
AU - Van Der Avoird, Ad
PY - 2013/12/19
Y1 - 2013/12/19
N2 - Ab initio calculations of the six-dimensional intermolecular potential have shown the benzene dimer to be an asymmetric top molecule at equilibrium with one benzene moiety forming the "stem" and the other a "tilted cap" in a T-shaped structure. Internal rotation of the cap about its C 6 axis is essentially free; the barriers for cap tilting and for internal rotation of the stem about its C6 axis are hindered by successively higher barriers. In previous work we have validated these theoretical results using Fourier transform microwave spectroscopy in conjunction with dynamics calculations. We have also measured the Stark effect, and despite the fact that the equilibrium structure is that of an asymmetric top, the assigned transitions involving K = 0 exhibit a second-order Stark effect whereas those involving K = 1 exhibit a first-order Stark effect. This is typical for a symmetric-top molecule, but anomalous for an asymmetric-top molecule. We use symmetry arguments to explain how this asymmetric-top molecule can have a first-order Stark effect in certain states that have excitation of cap internal rotation. Cap internal rotation is essentially the twisting of the monomers relative to each other about the intermolecular axis, and such torsional motion occurs in other asymmetric top dimers such as benzene-CO and benzene-H2O. These latter dimers will also have levels that exhibit a first-order Stark effect, which we can explain using our symmetry arguments.
AB - Ab initio calculations of the six-dimensional intermolecular potential have shown the benzene dimer to be an asymmetric top molecule at equilibrium with one benzene moiety forming the "stem" and the other a "tilted cap" in a T-shaped structure. Internal rotation of the cap about its C 6 axis is essentially free; the barriers for cap tilting and for internal rotation of the stem about its C6 axis are hindered by successively higher barriers. In previous work we have validated these theoretical results using Fourier transform microwave spectroscopy in conjunction with dynamics calculations. We have also measured the Stark effect, and despite the fact that the equilibrium structure is that of an asymmetric top, the assigned transitions involving K = 0 exhibit a second-order Stark effect whereas those involving K = 1 exhibit a first-order Stark effect. This is typical for a symmetric-top molecule, but anomalous for an asymmetric-top molecule. We use symmetry arguments to explain how this asymmetric-top molecule can have a first-order Stark effect in certain states that have excitation of cap internal rotation. Cap internal rotation is essentially the twisting of the monomers relative to each other about the intermolecular axis, and such torsional motion occurs in other asymmetric top dimers such as benzene-CO and benzene-H2O. These latter dimers will also have levels that exhibit a first-order Stark effect, which we can explain using our symmetry arguments.
UR - http://www.scopus.com/inward/record.url?scp=84890933775&partnerID=8YFLogxK
U2 - 10.1021/jp408076q
DO - 10.1021/jp408076q
M3 - Article
AN - SCOPUS:84890933775
VL - 117
SP - 13775
EP - 13778
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 50
ER -