DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: The NH stretching mode in ND3H+

Abstract

High-resolution rotationally resolved spectra of the N–H stretch vibrational mode (ν1) of jet-cooled ND3H+ ions are collected and analyzed in a sub-Doppler slit-jet infrared spectrometer. The isotopomeric ammonium ions are generated by proton transfer from H3+ to ND3 in a discharge of an ND3/H2 gas mixture, whereby the slit jet expansion cools the nascent ND3H+ ions into lower rotational states. Rotational assignments are confirmed by four-line combination differences that agree to within the spectrometer precision (9 MHz). Based on precision two-line ground-state combination differences and a symmetric top Hamiltonian, the B, DJ, and DJK rotational constants for the ground vibrational state of ND3H+ are determined with high precision for the first time. Approximate rotational constants for the ν1 excited state are also determined, with a band origin at 3316.8425(19) cm-1 and in remarkable (~0.1 cm-1) agreement with high level anharmonic theoretical predictions by Guo and co-workers [J. Phys. Chem. A, 120, 2185 (2016)]. Our results allow us to predict several low-J pure rotational transitions of ND3H+, which we hope will support future studies of this important ion in laboratory and astronomical rotational spectroscopy.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]
  1. Spectra Sensors, Houston, TX (United States)
  2. Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1610626
Alternate Identifier(s):
OSTI ID: 1476693; OSTI ID: 1924533
Grant/Contract Number:  
SC0002123; FG02-09ER16021
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 14; 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; Chemistry; Physics; Vibrational spectroscopy; Infrared spectroscopy; Interstellar medium; Isotopes; Ab initio coupled-cluster calculations; Rotational spectroscopy

Citation Formats

Chang, Chih-Hsuan, Scrape, Preston G., and Nesbitt, David J. Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: The NH stretching mode in ND3H+. United States: N. p., 2018. Web. doi:10.1063/1.5049603.
Chang, Chih-Hsuan, Scrape, Preston G., & Nesbitt, David J. Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: The NH stretching mode in ND3H+. United States. https://doi.org/10.1063/1.5049603
Chang, Chih-Hsuan, Scrape, Preston G., and Nesbitt, David J. Mon . "Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: The NH stretching mode in ND3H+". United States. https://doi.org/10.1063/1.5049603. https://www.osti.gov/servlets/purl/1610626.
@article{osti_1610626,
title = {Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: The NH stretching mode in ND3H+},
author = {Chang, Chih-Hsuan and Scrape, Preston G. and Nesbitt, David J.},
abstractNote = {High-resolution rotationally resolved spectra of the N–H stretch vibrational mode (ν1) of jet-cooled ND3H+ ions are collected and analyzed in a sub-Doppler slit-jet infrared spectrometer. The isotopomeric ammonium ions are generated by proton transfer from H3+ to ND3 in a discharge of an ND3/H2 gas mixture, whereby the slit jet expansion cools the nascent ND3H+ ions into lower rotational states. Rotational assignments are confirmed by four-line combination differences that agree to within the spectrometer precision (9 MHz). Based on precision two-line ground-state combination differences and a symmetric top Hamiltonian, the B, DJ, and DJK rotational constants for the ground vibrational state of ND3H+ are determined with high precision for the first time. Approximate rotational constants for the ν1 excited state are also determined, with a band origin at 3316.8425(19) cm-1 and in remarkable (~0.1 cm-1) agreement with high level anharmonic theoretical predictions by Guo and co-workers [J. Phys. Chem. A, 120, 2185 (2016)]. Our results allow us to predict several low-J pure rotational transitions of ND3H+, which we hope will support future studies of this important ion in laboratory and astronomical rotational spectroscopy.},
doi = {10.1063/1.5049603},
journal = {Journal of Chemical Physics},
number = 14,
volume = 149,
place = {United States},
year = {Mon Oct 08 00:00:00 EDT 2018},
month = {Mon Oct 08 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Concentration modulation spectroscopy with a pulsed slit supersonic discharge expansion source
journal, August 2001


Slit Discharge IR Spectroscopy of a Jet-Cooled Cyclopropyl Radical:  Structure and Intramolecular Tunneling Dynamics
journal, March 2006

  • Dong, Feng; Davis, Scott; Nesbitt, David J.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 9
  • DOI: 10.1021/jp053994u

Vibrations of the ammonium-d ion in ammonium tetrafluoroborate crystals at low temperatures
journal, July 1987

  • Roberts, Malcolm P.; Strauss, Herbert L.
  • The Journal of Physical Chemistry, Vol. 91, Issue 16
  • DOI: 10.1021/j100300a008

Accurate ab initio quartic force field and vibrational frequencies of the NH4+ ion and its deuterated forms
journal, August 1996


The abundances of nitrogen-containing molecules during pre-protostellar collapse
journal, August 2006

  • Flower, D. R.; Pineau des Forêts, G.; Walmsley, C. M.
  • Astronomy & Astrophysics, Vol. 456, Issue 1
  • DOI: 10.1051/0004-6361:20065375

Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν1) and antisymmetric (ν6) NH stretching modes in ND 2 H 2 +
journal, January 2018

  • Chang, Chih-Hsuan; Nesbitt, David J.
  • The Journal of Chemical Physics, Vol. 148, Issue 1
  • DOI: 10.1063/1.5003230

An intense slit discharge source of jet-cooled molecular ions and radicals (Trot < 30 K
journal, August 1996


Does metallic ammonium exist? (From old and new literature)
journal, August 1978


Gas phase production of NHD2 in L134N
text, January 2001


Rotation and Solvation of Ammonium Ion
journal, December 1987


IMPROVED DETERMINATION OF THE 1 0 -0 0 ROTATIONAL FREQUENCY OF NH 3 D + FROM THE HIGH-RESOLUTION SPECTRUM OF THE ν 4 INFRARED BAND
journal, June 2013


Detection of the Ammonium ion in Space
journal, June 2013


Structure of the ammonium radical from a rotationally resolved photoelectron spectrum
journal, April 1997

  • Signorell, R.; Palm, H.; Merkt, F.
  • The Journal of Chemical Physics, Vol. 106, Issue 16
  • DOI: 10.1063/1.473653

Rotation, solvation, and hydrogen bonding of aqueous ammonium ion
journal, March 1986

  • Perrin, Charles L.; Gipe, Robert K.
  • Journal of the American Chemical Society, Vol. 108, Issue 5
  • DOI: 10.1021/ja00265a044

Electron-Driven Acid-Base Chemistry: Proton Transfer from Hydrogen Chloride to Ammonia
journal, February 2008


Mechanism of Ammonia Transport by Amt/MEP/Rh: Structure of AmtB at 1.35 A
journal, September 2004


Infrared spectrum of the NH4-dn+ cation trapped in solid neon
journal, January 2005

  • Jacox, Marilyn E.; ThompsonGuest researcher, National, Warren E.
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 5
  • DOI: 10.1039/b414641g

Jet cooled spectroscopy of H2DO+: Barrier heights and isotope-dependent tunneling dynamics from H3O+ to D3O+
journal, October 2006

  • Dong, Feng; Nesbitt, David J.
  • The Journal of Chemical Physics, Vol. 125, Issue 14
  • DOI: 10.1063/1.2338520

PGOPHER: A program for simulating rotational, vibrational and electronic spectra
journal, January 2017


Does metallic ammonium exist?
journal, November 1975


Interstellar H 3 +
journal, November 2013


The ν4Band of Ammonium, NH+4
journal, September 1996

  • Park, Joonbum; Xia, Changhong; Selby, Stan
  • Journal of Molecular Spectroscopy, Vol. 179, Issue 1
  • DOI: 10.1006/jmsp.1996.0193

Detection of Triply Deuterated Ammonia in the Barnard 1 Cloud
journal, May 2002

  • Lis, D. C.; Roueff, E.; Gerin, M.
  • The Astrophysical Journal, Vol. 571, Issue 1
  • DOI: 10.1086/341132

A channel-like transporter for NH4+ on the symbiotic interface of N2-fixing plants
journal, December 1995

  • Tyerman, Stephen D.; Whitehead, Lynne F.; Day, David A.
  • Nature, Vol. 378, Issue 6557
  • DOI: 10.1038/378629a0

Ultrasensitive laser measurements without tears
journal, January 1997


Full-Dimensional Quantum Calculations of Vibrational Levels of NH 4 + and Isotopomers on An Accurate Ab Initio Potential Energy Surface
journal, April 2016

  • Yu, Hua-Gen; Han, Huixian; Guo, Hua
  • The Journal of Physical Chemistry A, Vol. 120, Issue 14
  • DOI: 10.1021/acs.jpca.6b01946

Interstellar deuterated ammonia: from NH 3 to ND 3
journal, July 2005


Difference-frequency laser spectroscopy of the ν 4 fundamental band of NH 3 D +
journal, October 1986

  • Nakanaga, T.; Amano, T.
  • Canadian Journal of Physics, Vol. 64, Issue 10
  • DOI: 10.1139/p86-240

The ν3 Fundamental in C2H2
journal, February 1993

  • Vanderauwera, J.; Hurtmans, D.; Carleer, M.
  • Journal of Molecular Spectroscopy, Vol. 157, Issue 2
  • DOI: 10.1006/jmsp.1993.1027

Ground State Rotational Lines of Doubly Deuterated Ammonia as Tracers of the Physical Conditions and Chemistry of Cold Interstellar Medium
journal, January 2006

  • Lis, D. C.; Gerin, M.; Roueff, E.
  • The Astrophysical Journal, Vol. 636, Issue 2
  • DOI: 10.1086/498077

Origin of the 6.85 $\mathsf{\mu}$m band near young stellar objects: The ammonium ion (NH 4^+ ) revisited
journal, January 2003


Gaseous ammonia and ammonium ions in the free troposphere
journal, May 1986


Gas‐Phase Production of NHD 2 in L134N
journal, June 2001

  • Rodgers, S. D.; Charnley, S. B.
  • The Astrophysical Journal, Vol. 553, Issue 2
  • DOI: 10.1086/320987

Spin-state chemistry of deuterated ammonia
journal, September 2015


A high resolution study of the ν 3 band of the ammonium ion (NH + 4 ) by velocity modulation laser absorption spectroscopy
journal, May 1984

  • Schäfer, Eckhard; Saykally, Richard J.; Robiette, Alan G.
  • The Journal of Chemical Physics, Vol. 80, Issue 9
  • DOI: 10.1063/1.447279

Infrared studies of molecular ions. I. The ν 3 band of NH 4 +
journal, September 1983

  • Crofton, Mark W.; Oka, Takeshi
  • The Journal of Chemical Physics, Vol. 79, Issue 6
  • DOI: 10.1063/1.446147

The ν 3 vibrational spectrum of the free ammonium ion (NH 4 + )
journal, September 1983

  • Schäfer, Eckhard; Begemann, Marianne H.; Gudeman, Christopher S.
  • The Journal of Chemical Physics, Vol. 79, Issue 6
  • DOI: 10.1063/1.446148

Velocity modulation infrared laser spectroscopy of molecular ions: The
journal, April 1989


Triply deuterated ammonia in NGC 1333
journal, June 2002

  • van der Tak, F. F. S.; Schilke, P.; Müller, H. S. P.
  • Astronomy & Astrophysics, Vol. 388, Issue 3
  • DOI: 10.1051/0004-6361:20020647

Laser spectroscopy of jet-cooled ethyl radical: Infrared studies in the CH2 stretch manifold
journal, January 2000

  • Davis, Scott; Uy, Dairene; Nesbitt, David J.
  • The Journal of Chemical Physics, Vol. 112, Issue 4
  • DOI: 10.1063/1.480746

Laboratory rotational ground state transitions of NH 3 D + and CF +
journal, September 2016


Observing the gas temperature drop in the high-density nucleus of L 1544
journal, May 2007


Works referencing / citing this record:

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

  • Scrape, Preston G.; Chang, Chih-Hsuan; Nesbitt, David J.
  • The Journal of Chemical Physics, Vol. 151, Issue 8
  • DOI: 10.1063/1.5113962

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

  • Doménech, José L.; Schlemmer, Stephan; Asvany, Oskar
  • The Astrophysical Journal, Vol. 866, Issue 2
  • DOI: 10.3847/1538-4357/aadf83