Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2=CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene

Jean Demaison, Norman C. Craig, Ranil Gurusinghe, Michael J. Tubergen, Heinz Dieter Rudolph, Laurent H. Coudert, Péter G. Szalay, A. Császár

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The ground-state rotational spectrum of propene-3-d1, CH2=CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of the plane (A). The energy difference between the two conformers was calculated to be 6.5 cm-1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for both conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground-state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground-state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.

Original languageEnglish
Pages (from-to)3155-3166
Number of pages12
JournalJournal of Physical Chemistry A
Volume121
Issue number16
DOIs
Publication statusPublished - Apr 27 2017

Fingerprint

Deuterium
microwave spectra
Ground state
deuterium
Fourier transforms
quadrupoles
Microwaves
Atoms
Microwave spectroscopy
ground state
Hydrogen
rotational spectra
hyperfine structure
atoms
hydrogen atoms
microwaves
propylene
energy
symmetry
spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2=CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene. / Demaison, Jean; Craig, Norman C.; Gurusinghe, Ranil; Tubergen, Michael J.; Rudolph, Heinz Dieter; Coudert, Laurent H.; Szalay, Péter G.; Császár, A.

In: Journal of Physical Chemistry A, Vol. 121, No. 16, 27.04.2017, p. 3155-3166.

Research output: Contribution to journalArticle

Demaison, Jean ; Craig, Norman C. ; Gurusinghe, Ranil ; Tubergen, Michael J. ; Rudolph, Heinz Dieter ; Coudert, Laurent H. ; Szalay, Péter G. ; Császár, A. / Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2=CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene. In: Journal of Physical Chemistry A. 2017 ; Vol. 121, No. 16. pp. 3155-3166.
@article{10572377d1c744758775e661c5032353,
title = "Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2=CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene",
abstract = "The ground-state rotational spectrum of propene-3-d1, CH2=CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of the plane (A). The energy difference between the two conformers was calculated to be 6.5 cm-1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for both conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground-state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground-state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.",
author = "Jean Demaison and Craig, {Norman C.} and Ranil Gurusinghe and Tubergen, {Michael J.} and Rudolph, {Heinz Dieter} and Coudert, {Laurent H.} and Szalay, {P{\'e}ter G.} and A. Cs{\'a}sz{\'a}r",
year = "2017",
month = "4",
day = "27",
doi = "10.1021/acs.jpca.7b01470",
language = "English",
volume = "121",
pages = "3155--3166",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "16",

}

TY - JOUR

T1 - Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2=CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene

AU - Demaison, Jean

AU - Craig, Norman C.

AU - Gurusinghe, Ranil

AU - Tubergen, Michael J.

AU - Rudolph, Heinz Dieter

AU - Coudert, Laurent H.

AU - Szalay, Péter G.

AU - Császár, A.

PY - 2017/4/27

Y1 - 2017/4/27

N2 - The ground-state rotational spectrum of propene-3-d1, CH2=CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of the plane (A). The energy difference between the two conformers was calculated to be 6.5 cm-1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for both conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground-state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground-state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.

AB - The ground-state rotational spectrum of propene-3-d1, CH2=CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of the plane (A). The energy difference between the two conformers was calculated to be 6.5 cm-1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for both conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground-state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground-state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.

UR - http://www.scopus.com/inward/record.url?scp=85020198114&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85020198114&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.7b01470

DO - 10.1021/acs.jpca.7b01470

M3 - Article

VL - 121

SP - 3155

EP - 3166

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 16

ER -