Abstract
The H2=CCD isotopic species of vinyl radical produced in a supersonic jet expansion by ultraviolet laser photolysis was studied by millimeter-wave spectroscopy. Due to the tunneling motion of the α deuteron, the ground state is split into two components, 0+ and 0-. Tunneling-rotation transitions connecting the lower (0+) and upper (0-) components of the tunneling doublet were observed in the frequency region of 184-334 GHz, including three R - and two Q -branch transitions. Three and two pure rotational transitions in the Ka =0 and 1 stacks, respectively, were also observed for each of the 0+ and 0- states in the frequency region of 52-159 GHz. Least-squares analysis of the observed frequencies for the tunneling-rotation and pure rotational transitions with well resolved hyperfine structures yielded a set of precise molecular constants, among which the tunneling splitting in the ground state was determined to be Δ E 0 =1187.234 (17) MHz, which is 1/14 that for H2 CCH. The potential barrier height derived from the observed tunneling splitting by an analysis of the tunneling dynamics using a one-dimensional model is 1545 cm -1, consistent with the value 1568 cm-1 obtained for the normal vinyl. The observed spectrum was found to be perturbed by a hyperfine interaction connecting ortho and para levels. The constant for the interaction, which we call the ortho-para mixing Fermi contact interaction, has been determined to be δ aF (β) =68.06 (53) MHz. This is believed to be the first definite detection of such an interaction. By this interaction the ortho and para states of H2=CCD are mixed up to about 0.1%. The constant is more than 1000 times larger than spin-rotation interaction constants that cause ortho-para mixing in closed shell molecules and suggests extremely rapid conversion between the ortho and para nuclear spin isomers of H2=CCD.
| Original language | English |
|---|---|
| Article number | 154303 |
| Journal | Journal of Chemical Physics |
| Volume | 133 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - Oct 21 2010 |
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All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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Millimeter-wave spectroscopy of H2=CCD : Tunneling splitting and ortho-para mixing interaction. / Hayashi, Masato; Harada, Kensuke; Lavrich, Richard; Tanaka, Takehiko; Tanaka, Keiichi.
In: Journal of Chemical Physics, Vol. 133, No. 15, 154303, 21.10.2010.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Millimeter-wave spectroscopy of H2=CCD
T2 - Tunneling splitting and ortho-para mixing interaction
AU - Hayashi, Masato
AU - Harada, Kensuke
AU - Lavrich, Richard
AU - Tanaka, Takehiko
AU - Tanaka, Keiichi
PY - 2010/10/21
Y1 - 2010/10/21
N2 - The H2=CCD isotopic species of vinyl radical produced in a supersonic jet expansion by ultraviolet laser photolysis was studied by millimeter-wave spectroscopy. Due to the tunneling motion of the α deuteron, the ground state is split into two components, 0+ and 0-. Tunneling-rotation transitions connecting the lower (0+) and upper (0-) components of the tunneling doublet were observed in the frequency region of 184-334 GHz, including three R - and two Q -branch transitions. Three and two pure rotational transitions in the Ka =0 and 1 stacks, respectively, were also observed for each of the 0+ and 0- states in the frequency region of 52-159 GHz. Least-squares analysis of the observed frequencies for the tunneling-rotation and pure rotational transitions with well resolved hyperfine structures yielded a set of precise molecular constants, among which the tunneling splitting in the ground state was determined to be Δ E 0 =1187.234 (17) MHz, which is 1/14 that for H2 CCH. The potential barrier height derived from the observed tunneling splitting by an analysis of the tunneling dynamics using a one-dimensional model is 1545 cm -1, consistent with the value 1568 cm-1 obtained for the normal vinyl. The observed spectrum was found to be perturbed by a hyperfine interaction connecting ortho and para levels. The constant for the interaction, which we call the ortho-para mixing Fermi contact interaction, has been determined to be δ aF (β) =68.06 (53) MHz. This is believed to be the first definite detection of such an interaction. By this interaction the ortho and para states of H2=CCD are mixed up to about 0.1%. The constant is more than 1000 times larger than spin-rotation interaction constants that cause ortho-para mixing in closed shell molecules and suggests extremely rapid conversion between the ortho and para nuclear spin isomers of H2=CCD.
AB - The H2=CCD isotopic species of vinyl radical produced in a supersonic jet expansion by ultraviolet laser photolysis was studied by millimeter-wave spectroscopy. Due to the tunneling motion of the α deuteron, the ground state is split into two components, 0+ and 0-. Tunneling-rotation transitions connecting the lower (0+) and upper (0-) components of the tunneling doublet were observed in the frequency region of 184-334 GHz, including three R - and two Q -branch transitions. Three and two pure rotational transitions in the Ka =0 and 1 stacks, respectively, were also observed for each of the 0+ and 0- states in the frequency region of 52-159 GHz. Least-squares analysis of the observed frequencies for the tunneling-rotation and pure rotational transitions with well resolved hyperfine structures yielded a set of precise molecular constants, among which the tunneling splitting in the ground state was determined to be Δ E 0 =1187.234 (17) MHz, which is 1/14 that for H2 CCH. The potential barrier height derived from the observed tunneling splitting by an analysis of the tunneling dynamics using a one-dimensional model is 1545 cm -1, consistent with the value 1568 cm-1 obtained for the normal vinyl. The observed spectrum was found to be perturbed by a hyperfine interaction connecting ortho and para levels. The constant for the interaction, which we call the ortho-para mixing Fermi contact interaction, has been determined to be δ aF (β) =68.06 (53) MHz. This is believed to be the first definite detection of such an interaction. By this interaction the ortho and para states of H2=CCD are mixed up to about 0.1%. The constant is more than 1000 times larger than spin-rotation interaction constants that cause ortho-para mixing in closed shell molecules and suggests extremely rapid conversion between the ortho and para nuclear spin isomers of H2=CCD.
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U2 - 10.1063/1.3478696
DO - 10.1063/1.3478696
M3 - Article
C2 - 20969382
AN - SCOPUS:78049254484
VL - 133
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 15
M1 - 154303
ER -