Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl Cyanide
The orientation and magnitude of the molecular electric dipole moment are key properties relevant to topics ranging from the nature of intermolecular interactions to the quantitative analysis of complex gas-phase mixtures, such as chemistry in astrophysical environments. Stark effect measurements on...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/4/1692 |
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| author | Zbigniew Kisiel Krzysztof Habdas |
| author_facet | Zbigniew Kisiel Krzysztof Habdas |
| author_sort | Zbigniew Kisiel |
| collection | DOAJ |
| description | The orientation and magnitude of the molecular electric dipole moment are key properties relevant to topics ranging from the nature of intermolecular interactions to the quantitative analysis of complex gas-phase mixtures, such as chemistry in astrophysical environments. Stark effect measurements on rotational spectra have been the method of choice for isolated molecules but have become less common with the practical disappearance of Stark modulation spectrometers. Their role has been taken over by supersonic expansion measurements within a Fabry-Perot resonator cavity, which introduces specific technical problems that need to be overcome. Several of the adopted solutions are described and compared. Presently, we report precise electric dipole moment determinations for the two most stable conformers of the selected molecules of confirmed or potential astrophysical relevance: <i>n</i>-propanol, <i>n</i>-butanol, and <i>n</i>-butyl cyanide. All dipole moment components have been precisely determined at supersonic expansion conditions by employing specially designed Stark electrodes and a computer program for fitting the measured Stark shifts, inclusive of cases with resolved nuclear quadrupole hyperfine structure. The experimental values are compared with suitable quantum chemistry computations. It is found that, among the tested levels of computation, vibrationally averaged dipole moments are the closest to the observation and the molecular values are, as in the lighter molecules in the series, largely determined by the hydroxyl or nitrile groups. |
| first_indexed | 2024-03-11T08:22:27Z |
| format | Article |
| id | doaj.art-a6459671da764d2082726e588b5ec7a9 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T08:22:27Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-a6459671da764d2082726e588b5ec7a92023-11-16T22:21:57ZengMDPI AGMolecules1420-30492023-02-01284169210.3390/molecules28041692Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl CyanideZbigniew Kisiel0Krzysztof Habdas1Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warszawa, PolandDepartment of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UKThe orientation and magnitude of the molecular electric dipole moment are key properties relevant to topics ranging from the nature of intermolecular interactions to the quantitative analysis of complex gas-phase mixtures, such as chemistry in astrophysical environments. Stark effect measurements on rotational spectra have been the method of choice for isolated molecules but have become less common with the practical disappearance of Stark modulation spectrometers. Their role has been taken over by supersonic expansion measurements within a Fabry-Perot resonator cavity, which introduces specific technical problems that need to be overcome. Several of the adopted solutions are described and compared. Presently, we report precise electric dipole moment determinations for the two most stable conformers of the selected molecules of confirmed or potential astrophysical relevance: <i>n</i>-propanol, <i>n</i>-butanol, and <i>n</i>-butyl cyanide. All dipole moment components have been precisely determined at supersonic expansion conditions by employing specially designed Stark electrodes and a computer program for fitting the measured Stark shifts, inclusive of cases with resolved nuclear quadrupole hyperfine structure. The experimental values are compared with suitable quantum chemistry computations. It is found that, among the tested levels of computation, vibrationally averaged dipole moments are the closest to the observation and the molecular values are, as in the lighter molecules in the series, largely determined by the hydroxyl or nitrile groups.https://www.mdpi.com/1420-3049/28/4/1692electric dipole momentssupersonic expansionrotational spectroscopymolecular structurehyperfine splitting |
| spellingShingle | Zbigniew Kisiel Krzysztof Habdas Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl Cyanide Molecules electric dipole moments supersonic expansion rotational spectroscopy molecular structure hyperfine splitting |
| title | Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl Cyanide |
| title_full | Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl Cyanide |
| title_fullStr | Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl Cyanide |
| title_full_unstemmed | Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl Cyanide |
| title_short | Electric Dipole Moments from Stark Effect in Supersonic Expansion: <i>n</i>-Propanol, <i>n</i>-Butanol, and <i>n</i>-Butyl Cyanide |
| title_sort | electric dipole moments from stark effect in supersonic expansion i n i propanol i n i butanol and i n i butyl cyanide |
| topic | electric dipole moments supersonic expansion rotational spectroscopy molecular structure hyperfine splitting |
| url | https://www.mdpi.com/1420-3049/28/4/1692 |
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