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Title: Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν 1) and antisymmetric (ν 6) NH stretching modes in ND 2H 2 +

Abstract

Sub-Doppler infrared rovibrational transitions in the symmetric (v1) and antisymmetric (v6) NH stretch modes of the isotopomerically substituted ND 2H 2 + ammonium cation are reported for the first time in a slit jet discharge supersonic expansion spectrometer. The partially H/D substituted cation is generated by selective isotopic exchange of ND 3 with H 2O to form NHD 2, followed by protonation with H3+ formed in the NHD2/H2/Ne slit-jet discharge expansion environment. Rotational assignment for ND 2H 2 + is confirmed rigorously by four line ground state combination differences, which agree to be within the sub-Doppler precision in the slit jet (∼9 MHz). Observation of both b-type (ν1) and c-type (ν6) bands enables high precision determination of the ground and vibrationally excited state rotational constants. From an asymmetric top Watson Hamiltonian analysis, the ground state constants are found to be A" = 4.856 75(4) cm-1, B" = 3.968 29(4) cm-1, and C" = 3.446 67(6) cm-1, with band origins at 3297.5440(1) and 3337.9050(1) cm-1 for the v1 and v6 modes, respectively. Lastly, this work permits prediction of precision microwave/mm-wave transitions, which should be invaluable in facilitating ongoing spectroscopic searches for partially deuterated ammonium cations in interstellar clouds and star-forming regionsmore » of the interstellar medium« less

Authors:
 [1];  [1]
  1. Univ. of Colorado, Boulder, CO (United States). JILA, National Inst. of Standards and Technology, Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1512942
Alternate Identifier(s):
OSTI ID: 1415507
Grant/Contract Number:  
SC0002123; FG02-09ER16021
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 79 ASTRONOMY AND ASTROPHYSICS

Citation Formats

Chang, Chih-Hsuan, and Nesbitt, David J. Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν1) and antisymmetric (ν6) NH stretching modes in ND2H2+. United States: N. p., 2019. Web. doi:10.1063/1.5003230.
Chang, Chih-Hsuan, & Nesbitt, David J. Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν1) and antisymmetric (ν6) NH stretching modes in ND2H2+. United States. https://doi.org/10.1063/1.5003230
Chang, Chih-Hsuan, and Nesbitt, David J. Wed . "Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν1) and antisymmetric (ν6) NH stretching modes in ND2H2+". United States. https://doi.org/10.1063/1.5003230. https://www.osti.gov/servlets/purl/1512942.
@article{osti_1512942,
title = {Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν1) and antisymmetric (ν6) NH stretching modes in ND2H2+},
author = {Chang, Chih-Hsuan and Nesbitt, David J.},
abstractNote = {Sub-Doppler infrared rovibrational transitions in the symmetric (v1) and antisymmetric (v6) NH stretch modes of the isotopomerically substituted ND2H2+ ammonium cation are reported for the first time in a slit jet discharge supersonic expansion spectrometer. The partially H/D substituted cation is generated by selective isotopic exchange of ND3 with H2O to form NHD2, followed by protonation with H3+ formed in the NHD2/H2/Ne slit-jet discharge expansion environment. Rotational assignment for ND2H2+ is confirmed rigorously by four line ground state combination differences, which agree to be within the sub-Doppler precision in the slit jet (∼9 MHz). Observation of both b-type (ν1) and c-type (ν6) bands enables high precision determination of the ground and vibrationally excited state rotational constants. From an asymmetric top Watson Hamiltonian analysis, the ground state constants are found to be A" = 4.856 75(4) cm-1, B" = 3.968 29(4) cm-1, and C" = 3.446 67(6) cm-1, with band origins at 3297.5440(1) and 3337.9050(1) cm-1 for the v1 and v6 modes, respectively. Lastly, this work permits prediction of precision microwave/mm-wave transitions, which should be invaluable in facilitating ongoing spectroscopic searches for partially deuterated ammonium cations in interstellar clouds and star-forming regions of the interstellar medium},
doi = {10.1063/1.5003230},
url = {https://www.osti.gov/biblio/1512942}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 1,
volume = 148,
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 2 works
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Figures / Tables:

FIG. 1 FIG. 1: Vibrational motion of the ND 2H 2 + ammonium cation in the (a) NH symmetric ($$ν$$ 1) and (b) antisymmetric ($$ν$$ 6) modes and associated vibration transition dipole moment orientation.

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    Works referencing / citing this record:

    Nanoporous Palladium Hydride for Electrocatalytic N 2 Reduction under Ambient Conditions
    journal, January 2020


    Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: The NH stretching mode in ND 3 H +
    journal, October 2018


    Suppressed-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: ν1 and ν4 NH stretching modes in NH 3 D +
    journal, August 2019


    Accurate Rotational Rest Frequencies for Ammonium Ion Isotopologues
    journal, October 2018