Details
| Original language | English |
|---|---|
| Pages (from-to) | 204-209 |
| Number of pages | 6 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 19 |
| Issue number | 1 |
| Early online date | 16 Nov 2016 |
| Publication status | Published - 7 Jan 2017 |
Abstract
Upon supersonic expansion, formic acid and cyclobutanone (CBU) form a molecular cluster in which the two constituent molecules, linked by OH⋯O and CH⋯O hydrogen bonds, undergo a rapid interconversion between two equivalent forms. The tunneling motion takes place through the rupture and reformation of the C-H⋯O hydrogen bond between the carbonyl oxygen of HCOOH and one of the two hydrogen atoms of the methylenic group adjacent to the cyclobutanone keto group. From the microwave spectra, tunneling energy splittings (ΔE01) have been determined for the parent (1122.756(3) MHz), DCOOH⋯CBU (1084.538(1) MHz) and HCOOD⋯CBU (1180.282(4) MHz) isotopic species. From these splittings, the potential barrier to interconversion has been calculated to be B2 = 39.7(5) cm-1. The tunneling pathway is an asymmetric butterfly-like motion between the two moieties of the adduct, with a barrier at a configuration in which the ring plane of cyclobutanone is coplanar with formic acid.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- General Physics and Astronomy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Physical Chemistry Chemical Physics, Vol. 19, No. 1, 07.01.2017, p. 204-209.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - A butterfly motion of formic acid and cyclobutanone in the 1:1 hydrogen bonded molecular cluster
AU - Evangelisti, Luca
AU - Spada, Lorenzo
AU - Li, Weixing
AU - Blanco, Susana
AU - López, Juan Carlos
AU - Lesarri, Alberto
AU - Grabow, Jens Uwe
AU - Caminati, Walther
N1 - Funding information: We thank the Italian MIUR (PRIN project 2010ERFKXL-001) and the University of Bologna (RFO) for financial support. We also thank funding from the Spanish MINECO-FEDER (CTQ2015-68148-C2-2-P) and the Junta de Castilla y León (UNVA-13-3E-2103).
PY - 2017/1/7
Y1 - 2017/1/7
N2 - Upon supersonic expansion, formic acid and cyclobutanone (CBU) form a molecular cluster in which the two constituent molecules, linked by OH⋯O and CH⋯O hydrogen bonds, undergo a rapid interconversion between two equivalent forms. The tunneling motion takes place through the rupture and reformation of the C-H⋯O hydrogen bond between the carbonyl oxygen of HCOOH and one of the two hydrogen atoms of the methylenic group adjacent to the cyclobutanone keto group. From the microwave spectra, tunneling energy splittings (ΔE01) have been determined for the parent (1122.756(3) MHz), DCOOH⋯CBU (1084.538(1) MHz) and HCOOD⋯CBU (1180.282(4) MHz) isotopic species. From these splittings, the potential barrier to interconversion has been calculated to be B2 = 39.7(5) cm-1. The tunneling pathway is an asymmetric butterfly-like motion between the two moieties of the adduct, with a barrier at a configuration in which the ring plane of cyclobutanone is coplanar with formic acid.
AB - Upon supersonic expansion, formic acid and cyclobutanone (CBU) form a molecular cluster in which the two constituent molecules, linked by OH⋯O and CH⋯O hydrogen bonds, undergo a rapid interconversion between two equivalent forms. The tunneling motion takes place through the rupture and reformation of the C-H⋯O hydrogen bond between the carbonyl oxygen of HCOOH and one of the two hydrogen atoms of the methylenic group adjacent to the cyclobutanone keto group. From the microwave spectra, tunneling energy splittings (ΔE01) have been determined for the parent (1122.756(3) MHz), DCOOH⋯CBU (1084.538(1) MHz) and HCOOD⋯CBU (1180.282(4) MHz) isotopic species. From these splittings, the potential barrier to interconversion has been calculated to be B2 = 39.7(5) cm-1. The tunneling pathway is an asymmetric butterfly-like motion between the two moieties of the adduct, with a barrier at a configuration in which the ring plane of cyclobutanone is coplanar with formic acid.
UR - http://www.scopus.com/inward/record.url?scp=85015939530&partnerID=8YFLogxK
U2 - 10.1039/c6cp06941j
DO - 10.1039/c6cp06941j
M3 - Article
AN - SCOPUS:85015939530
VL - 19
SP - 204
EP - 209
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 1
ER -