Details
| Original language | English |
|---|---|
| Pages (from-to) | 16-22 |
| Number of pages | 7 |
| Journal | Journal of molecular spectroscopy |
| Volume | 268 |
| Issue number | 1-2 |
| Publication status | Published - Jul 2011 |
Abstract
The rotational spectrum of fumaric acid was studied in a pulsed supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. The ground-state rotational constants, centrifugal distortion constants and the electric dipole moment of the molecule were determined at high accuracy. Agreement of experimental values with those predicted by ab initio methods for the s-cis,s-trans conformer, one of the three plausible conformers in the gas-phase, has unambiguously confirmed the presence of this conformer in the cold jet. The semi-experimental equilibrium rotational constants Be(i) derived from the experimental values B0(i) and the rovibrational corrections from the MP2/cc-pVTZ cubic force field calculation are in excellent agreement with the high-level ab initio values. The ab initio geometries of low-energy conformers s-cis,s-cis, s-cis,s-trans, and s-trans,s-trans were optimized at the CCSD(T) level of theory. It was shown that the structural and spectroscopic parameters (i.e. bond lengths, rotational constants, and vibrational frequencies) from experimental and theoretical methods are compatible when anharmonic effects are taken into account.
Keywords
- Dipole moment, Force field, Microwave spectroscopy, Rotational spectroscopy, Structure, Supersonic-jet
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Atomic and Molecular Physics, and Optics
- Chemistry(all)
- Spectroscopy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Journal of molecular spectroscopy, Vol. 268, No. 1-2, 07.2011, p. 16-22.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Microwave rotational spectrum and ab initio equilibrium structure of fumaric acid
T2 - Anharmonicity bridging the molecular characterizations
AU - Vogt, Natalja
AU - Rajappan Nair, K. P.
AU - Vogt, Jürgen
AU - Grabow, Jens Uwe
N1 - Funding Information: We gratefully acknowledge support from the Deutsche Forschungsgemeinschaft (DFG), the Land Niedersachsen, and the Dr. Barbara Mez-Starck Foundation, and especially the assistance of J. Demaison in the treatment of anharmonic effects.
PY - 2011/7
Y1 - 2011/7
N2 - The rotational spectrum of fumaric acid was studied in a pulsed supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. The ground-state rotational constants, centrifugal distortion constants and the electric dipole moment of the molecule were determined at high accuracy. Agreement of experimental values with those predicted by ab initio methods for the s-cis,s-trans conformer, one of the three plausible conformers in the gas-phase, has unambiguously confirmed the presence of this conformer in the cold jet. The semi-experimental equilibrium rotational constants Be(i) derived from the experimental values B0(i) and the rovibrational corrections from the MP2/cc-pVTZ cubic force field calculation are in excellent agreement with the high-level ab initio values. The ab initio geometries of low-energy conformers s-cis,s-cis, s-cis,s-trans, and s-trans,s-trans were optimized at the CCSD(T) level of theory. It was shown that the structural and spectroscopic parameters (i.e. bond lengths, rotational constants, and vibrational frequencies) from experimental and theoretical methods are compatible when anharmonic effects are taken into account.
AB - The rotational spectrum of fumaric acid was studied in a pulsed supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. The ground-state rotational constants, centrifugal distortion constants and the electric dipole moment of the molecule were determined at high accuracy. Agreement of experimental values with those predicted by ab initio methods for the s-cis,s-trans conformer, one of the three plausible conformers in the gas-phase, has unambiguously confirmed the presence of this conformer in the cold jet. The semi-experimental equilibrium rotational constants Be(i) derived from the experimental values B0(i) and the rovibrational corrections from the MP2/cc-pVTZ cubic force field calculation are in excellent agreement with the high-level ab initio values. The ab initio geometries of low-energy conformers s-cis,s-cis, s-cis,s-trans, and s-trans,s-trans were optimized at the CCSD(T) level of theory. It was shown that the structural and spectroscopic parameters (i.e. bond lengths, rotational constants, and vibrational frequencies) from experimental and theoretical methods are compatible when anharmonic effects are taken into account.
KW - Dipole moment
KW - Force field
KW - Microwave spectroscopy
KW - Rotational spectroscopy
KW - Structure
KW - Supersonic-jet
UR - http://www.scopus.com/inward/record.url?scp=80052271903&partnerID=8YFLogxK
U2 - 10.1016/j.jms.2011.03.027
DO - 10.1016/j.jms.2011.03.027
M3 - Article
AN - SCOPUS:80052271903
VL - 268
SP - 16
EP - 22
JO - Journal of molecular spectroscopy
JF - Journal of molecular spectroscopy
SN - 0022-2852
IS - 1-2
ER -