skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Reinterpreting the infrared spectrum of H + HCN: Methylene amidogen radical and its coproducts

Abstract

The methylene amidogen radical (H 2CN) plays a role in high-energy material combustion and extraterresterial atmospheres. Recent theoretical work has struggled to match experimental assignments for its CN and antisymmetric CH 2 stretching frequencies (ν 2 and ν 5), which were reported to occur at 1725 and 3103 cm –1. Herein, we compute the vibrational energy levels of this molecule by extrapolating quadruples-level coupled- cluster theory to the complete basis limit and adding corrections for vibrational anharmonicity. This level of theory predicts that ν 2 and ν 5 should occur at 1646 and 2892 cm –1, at odds with the experimental assignments. To investigate the possibility of defects in our theoretical treatment, we analyze the sensitivity of our approach to each of its contributing approximations. Our analysis suggests that the observed deviation from experiment is too large to be explained as an accumulation of errors, leading us to conclude that these transitions were misassigned. To help resolve this discrepancy, we investigate possible byproducts of the H + HCN reaction, which was the source of H 2CN in the original experiment. In particular, we predict vibrational spectra for cis-HCNH, trans-HCNH, and H 2CNH using high-level coupled-cluster computations. Based on these results,more » we reassign the transition at 1725 cm –1 to ν 3 of trans-HCNH, yielding excellent agreement. Supporting this identification, we assign a known contaminant peak at 886 cm –1 to ν 5 of the same conformer. Our computations suggest that the peak observed at 3103 cm –1, however, does not belong to any of the aforementioned species. To facilitate further investigation, we use structure and bonding arguments to narrow the range of possible candidates. Furthermore, these arguments lead us to tentatively put forth formaldazine [(H 2CN) 2] as a suggestion for further study, which we support with additional computations.« less

Authors:
 [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [1]; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
  2. Univ. of Georgia, Athens, GA (United States); Messiah College, Mechanicsburg, PA (United States)
  3. Univ. of Georgia, Athens, GA (United States); Federal Univ. of Sao Paulo, Sao Paulo (Brazil)
  4. Univ. of Georgia, Athens, GA (United States); Biola Univ., La Mirada, CA (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1468296
Alternate Identifier(s):
OSTI ID: 1415508
Grant/Contract Number:  
SC0018412; SC0015512
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:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Wiens, Avery E., Copan, Andreas V., Rossomme, Elliot C., Aroeira, Gustavo J. R., Bernstein, Olivia M., Agarwal, Jay, and Schaefer, Henry F. Reinterpreting the infrared spectrum of H + HCN: Methylene amidogen radical and its coproducts. United States: N. p., 2018. Web. doi:10.1063/1.5004984.
Wiens, Avery E., Copan, Andreas V., Rossomme, Elliot C., Aroeira, Gustavo J. R., Bernstein, Olivia M., Agarwal, Jay, & Schaefer, Henry F. Reinterpreting the infrared spectrum of H + HCN: Methylene amidogen radical and its coproducts. United States. doi:10.1063/1.5004984.
Wiens, Avery E., Copan, Andreas V., Rossomme, Elliot C., Aroeira, Gustavo J. R., Bernstein, Olivia M., Agarwal, Jay, and Schaefer, Henry F. Wed . "Reinterpreting the infrared spectrum of H + HCN: Methylene amidogen radical and its coproducts". United States. doi:10.1063/1.5004984. https://www.osti.gov/servlets/purl/1468296.
@article{osti_1468296,
title = {Reinterpreting the infrared spectrum of H + HCN: Methylene amidogen radical and its coproducts},
author = {Wiens, Avery E. and Copan, Andreas V. and Rossomme, Elliot C. and Aroeira, Gustavo J. R. and Bernstein, Olivia M. and Agarwal, Jay and Schaefer, Henry F.},
abstractNote = {The methylene amidogen radical (H2CN) plays a role in high-energy material combustion and extraterresterial atmospheres. Recent theoretical work has struggled to match experimental assignments for its CN and antisymmetric CH2 stretching frequencies (ν2 and ν5), which were reported to occur at 1725 and 3103 cm–1. Herein, we compute the vibrational energy levels of this molecule by extrapolating quadruples-level coupled- cluster theory to the complete basis limit and adding corrections for vibrational anharmonicity. This level of theory predicts that ν2 and ν5 should occur at 1646 and 2892 cm–1, at odds with the experimental assignments. To investigate the possibility of defects in our theoretical treatment, we analyze the sensitivity of our approach to each of its contributing approximations. Our analysis suggests that the observed deviation from experiment is too large to be explained as an accumulation of errors, leading us to conclude that these transitions were misassigned. To help resolve this discrepancy, we investigate possible byproducts of the H + HCN reaction, which was the source of H2CN in the original experiment. In particular, we predict vibrational spectra for cis-HCNH, trans-HCNH, and H2CNH using high-level coupled-cluster computations. Based on these results, we reassign the transition at 1725 cm–1 to ν3 of trans-HCNH, yielding excellent agreement. Supporting this identification, we assign a known contaminant peak at 886 cm–1 to ν5 of the same conformer. Our computations suggest that the peak observed at 3103 cm–1, however, does not belong to any of the aforementioned species. To facilitate further investigation, we use structure and bonding arguments to narrow the range of possible candidates. Furthermore, these arguments lead us to tentatively put forth formaldazine [(H2CN)2] as a suggestion for further study, which we support with additional computations.},
doi = {10.1063/1.5004984},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 1,
volume = 148,
place = {United States},
year = {2018},
month = {1}
}

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

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1. FIG. 1.: Planar equilibrium molecular structure for the ground (X̃ 2/B2) electronic state of H2CN, optimized at the CCSDT(Q)/CBS level of theory.

Save / Share:

Works referenced in this record:

Psi4 1.1: An Open-Source Electronic Structure Program Emphasizing Automation, Advanced Libraries, and Interoperability
journal, June 2017

  • Parrish, Robert M.; Burns, Lori A.; Smith, Daniel G. A.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 7
  • DOI: 10.1021/acs.jctc.7b00174

Nitramine propellant ignition and combustion research
journal, January 1991

  • Alexander, M. H.; Dagdigian, P. J.; Jacox, M. E.
  • Progress in Energy and Combustion Science, Vol. 17, Issue 4
  • DOI: 10.1016/0360-1285(91)90005-8

Representing Global Reactive Potential Energy Surfaces Using Gaussian Processes
journal, March 2017

  • Kolb, Brian; Marshall, Paul; Zhao, Bin
  • The Journal of Physical Chemistry A, Vol. 121, Issue 13
  • DOI: 10.1021/acs.jpca.7b01182

Molpro: a general-purpose quantum chemistry program package: Molpro
journal, July 2011

  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
  • DOI: 10.1002/wcms.82

HCN formation on Jupiter: The coupled photochemistry of ammonia and acetylene
journal, June 1983


Fourier transform infrared spectrum of CH2NH: The ν1 band
journal, July 1985


In pursuit of the ab initio limit for conformational energy prototypes
journal, June 1998

  • Császár, Attila G.; Allen, Wesley D.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 108, Issue 23
  • DOI: 10.1063/1.476449

Examining the ground and first excited states of methyl peroxy radical with high-level coupled-cluster theory
journal, July 2015


Relativistic Internally Contracted Multireference Electron Correlation Methods
journal, September 2015

  • Shiozaki, Toru; Mizukami, Wataru
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 10
  • DOI: 10.1021/acs.jctc.5b00754

Spectroscopic effects of conical intersections of molecular potential energy surfaces
journal, July 1981


Accurate vibrational spectra and magnetic properties of organic free radicals: The case of H2CN
journal, June 2005

  • Barone, Vincenzo; Carbonniere, Philippe; Pouchan, Claude
  • The Journal of Chemical Physics, Vol. 122, Issue 22
  • DOI: 10.1063/1.1924592

Infrared band intensities of formaldehyde and formaldehyde‐ d 2
journal, April 1982

  • Nakanaga, Taisuke; Kondo, Shigeo; Saëki, Shinnosuke
  • The Journal of Chemical Physics, Vol. 76, Issue 8
  • DOI: 10.1063/1.443527

Multiconfiguration Self-Consistent Field and Multireference Configuration Interaction Methods and Applications
journal, December 2011

  • Szalay, Péter G.; Müller, Thomas; Gidofalvi, Gergely
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200137a

The Raman Spectrum of Ethylene
journal, August 1956

  • Feldman, T.; Romanko, J.; Welsh, H. L.
  • Canadian Journal of Physics, Vol. 34, Issue 8
  • DOI: 10.1139/p56-085

Higher excitations in coupled-cluster theory
journal, August 2001

  • Kállay, Mihály; Surján, Péter R.
  • The Journal of Chemical Physics, Vol. 115, Issue 7
  • DOI: 10.1063/1.1383290

Experimental and Theoretical Study of the Electronic Spectrum of the Methylene Amidogen Radical (H 2 CN):  Verification of the 2 A 12 B 2 Assignment
journal, June 2006

  • Teslja, Alexey; Dagdigian, Paul J.; Banck, Michael
  • The Journal of Physical Chemistry A, Vol. 110, Issue 25
  • DOI: 10.1021/jp061578j

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

An efficient internally contracted multiconfiguration–reference configuration interaction method
journal, November 1988

  • Werner, Hans‐Joachim; Knowles, Peter J.
  • The Journal of Chemical Physics, Vol. 89, Issue 9
  • DOI: 10.1063/1.455556

The spectroscopy of molecular reaction intermediates trapped in the solid rare gases
journal, January 2002

  • Jacox, Marilyn E.
  • Chemical Society Reviews, Vol. 31, Issue 2
  • DOI: 10.1039/b102907j

Excited state dynamics of H2CN radicals
journal, November 1999


Theoretical Investigation of the Structure and Vibrational Spectrum of the Electronic Ground State X̃( 1 A‘) of HSiCl
journal, May 2002

  • Vázquez, J.; Stanton, John F.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 17
  • DOI: 10.1021/jp013761c

Approximate treatment of higher excitations in coupled-cluster theory
journal, December 2005

  • Kállay, Mihály; Gauss, Jürgen
  • The Journal of Chemical Physics, Vol. 123, Issue 21
  • DOI: 10.1063/1.2121589

A CASSCF and CASPT2 Study on the Excited States of s-trans -Formaldazine
journal, September 2008

  • Luo, Cheng; Duan, Xue-mei; Liu, Jing-yao
  • The Journal of Physical Chemistry A, Vol. 112, Issue 38
  • DOI: 10.1021/jp805081h

Parallelization Strategy for Large-Scale Vibronic Coupling Calculations
journal, October 2014

  • Rabidoux, Scott M.; Eijkhout, Victor; Stanton, John F.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 51
  • DOI: 10.1021/jp507880q

Benchmark calculations for molecules in the gas phase: State-of-the-art coupled-cluster computations
journal, March 2010

  • Puzzarini, Cristina; Barone, Vincenzo
  • International Journal of Quantum Chemistry, Vol. 110, Issue 3
  • DOI: 10.1002/qua.22132

The microwave spectrum of the CH2N radical in the X̃ 2B2 ground electronic state
journal, March 1992

  • Yamamoto, Satoshi; Saito, Shuji
  • The Journal of Chemical Physics, Vol. 96, Issue 6
  • DOI: 10.1063/1.461871

Photodissociation of formaldoxime and its methylated homologs: search for methylamidogen radical fluorescence
journal, August 1989

  • Dagdigian, Paul J.; Anderson, William R.; Sausa, Rosario
  • The Journal of Physical Chemistry, Vol. 93, Issue 16
  • DOI: 10.1021/j100353a024

Electron spin resonance study of the photolysis of formmaldazine
journal, January 1971

  • Kamachi, Mikiharu; Kuwata, Keiji; Murahashi, Shunsuke
  • The Journal of Physical Chemistry, Vol. 75, Issue 1
  • DOI: 10.1021/j100671a028

High resolution infrared spectrum of methyleneimine, CH 2 NH,in the 3 μm region
journal, September 1985

  • Halonen, Lauri; Duxbury, Geoffrey
  • The Journal of Chemical Physics, Vol. 83, Issue 5
  • DOI: 10.1063/1.449351

Coupled-cluster methods including noniterative corrections for quadruple excitations
journal, August 2005

  • Bomble, Yannick J.; Stanton, John F.; Kállay, Mihály
  • The Journal of Chemical Physics, Vol. 123, Issue 5
  • DOI: 10.1063/1.1950567

The infrared spectrum of methylenimine
journal, June 1975


Configuration interaction calculations on the nitrogen molecule
journal, January 1974

  • Langhoff, Stephen R.; Davidson, Ernest R.
  • International Journal of Quantum Chemistry, Vol. 8, Issue 1
  • DOI: 10.1002/qua.560080106

Neutral rare-gas containing charge-transfer molecules in solid matrices. III. HXeCN, HXeNC, and HKrCN in Kr and Xe
journal, July 1998

  • Pettersson, Mika; Lundell, Jan; Khriachtchev, Leonid
  • The Journal of Chemical Physics, Vol. 109, Issue 2
  • DOI: 10.1063/1.476599

Spectroscopic and Kinetic Investigation of Methylene Amidogen by Cavity Ring-Down Spectroscopy
journal, April 2003

  • Nizamov, Boris; Dagdigian, Paul J.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 13
  • DOI: 10.1021/jp022197i

Predissociation of the Schumann-Runge bands of O2
journal, May 1975


Spin-restricted open-shell coupled-cluster theory
journal, December 1997

  • Szalay, Péter G.; Gauss, Jürgen
  • The Journal of Chemical Physics, Vol. 107, Issue 21
  • DOI: 10.1063/1.475220

The diagonal correction to the Born–Oppenheimer approximation: Its effect on the singlet–triplet splitting of CH 2 and other molecular effects
journal, April 1986

  • Handy, Nicholas C.; Yamaguchi, Yukio; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 84, Issue 8
  • DOI: 10.1063/1.450020

ESR Detection of the Cyanogen and Methylene Imino Free Radicals
journal, April 1962

  • Cochran, Edward L.; Adrian, Frank J.; Bowers, Vernon A.
  • The Journal of Chemical Physics, Vol. 36, Issue 7
  • DOI: 10.1063/1.1701294

Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories
journal, September 1994


Carbon-13 hyperfine constants of methyleneamidogen, hydroxymethyleneamidogen and aminooxomethyl radicals
journal, June 1988

  • McManus, Hugh J.; Fessenden, Richard W.; Chipman, Daniel M.
  • The Journal of Physical Chemistry, Vol. 92, Issue 13
  • DOI: 10.1021/j100324a019

Application of systematic sequences of wave functions to the water dimer
journal, April 1992

  • Feller, David
  • The Journal of Chemical Physics, Vol. 96, Issue 8
  • DOI: 10.1063/1.462652

New theoretical evidence for the nonlinearity of the triplet ground state of methylene
journal, August 1970

  • Bender, Charles F.; Schaefer, Henry F.
  • Journal of the American Chemical Society, Vol. 92, Issue 16
  • DOI: 10.1021/ja00719a039

Electronic Absorption Spectra of Methanal Azine and the Methyleniminyl Free Radical
journal, March 1968

  • Ogilvie, J. F.; Horne, D. G.
  • The Journal of Chemical Physics, Vol. 48, Issue 5
  • DOI: 10.1063/1.1669419

The heat of formation of NCO
journal, September 1993

  • East, Allan L. L.; Allen, Wesley D.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466062

Methylene: A Paradigm for Computational Quantum Chemistry
journal, March 1986


Cyanovinyl radical: an illustration of the poor performance of unrestricted perturbation theory and density functional theory procedures in calculating radical stabilization energies
journal, June 1999

  • Parkinson, Christopher J.; Mayer, Paul M.; Radom, Leo
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 102, Issue 1-6
  • DOI: 10.1007/s002140050477

The puckering inversion barrier and vibrational spectrum of cyclopentene. A scaled quantum mechanical force field algorithm
journal, August 1992

  • Allen, Wesley D.; Csaszar, Attila G.; Horner, David A.
  • Journal of the American Chemical Society, Vol. 114, Issue 17
  • DOI: 10.1021/ja00043a032

Pyrolysis of amines: Infrared spectrum of methyleneimine
journal, May 1984

  • Hamada, Yoshiaki; Hashiguchi, Kazuko; Tsuboi, Masamichi
  • Journal of Molecular Spectroscopy, Vol. 105, Issue 1
  • DOI: 10.1016/0022-2852(84)90104-8

Detection of a new interstellar molecule, H2CN
journal, May 1994

  • Ohishi, Masatoshi; McGonagle, Douglas; Irvine, William M.
  • The Astrophysical Journal, Vol. 427
  • DOI: 10.1086/187362

Chemical Reactions in Energetic Materials
journal, October 1992


Vibrational and electronic spectra of the hydrogen atom + hydrogen cyanide reaction products trapped in solid argon
journal, December 1987

  • Jacox, Marilyn E.
  • The Journal of Physical Chemistry, Vol. 91, Issue 27
  • DOI: 10.1021/j100311a008

Non-iterative fifth-order triple and quadruple excitation energy corrections in correlated methods
journal, February 1990


A fifth-order perturbation comparison of electron correlation theories
journal, May 1989


Measurement of the photoionization spectra and ionization thresholds of the methyleneamidogen and methyleneamidogen-d2 radicals
journal, October 1991

  • Nesbitt, F. L.; Marston, G.; Stief, L. J.
  • The Journal of Physical Chemistry, Vol. 95, Issue 20
  • DOI: 10.1021/j100173a012

A remarkable large effect of spin contamination on calculated vibrational frequencies
journal, June 1990


The infrared spectrum of thioformaldehyde
journal, September 1971


Electron-spin-resonance studies of HMX pyrolysis products
journal, January 1979


Infrared overtone spectroscopy and unimolecular decay dynamics of peroxynitrous acid
journal, March 2005

  • Konen, Ian M.; Pollack, Ilana B.; Li, Eunice X. J.
  • The Journal of Chemical Physics, Vol. 122, Issue 9
  • DOI: 10.1063/1.1854094

Basis-set convergence of correlated calculations on water
journal, June 1997

  • Helgaker, Trygve; Klopper, Wim; Koch, Henrik
  • The Journal of Chemical Physics, Vol. 106, Issue 23
  • DOI: 10.1063/1.473863

Perturbative treatment of triple excitations in internally contracted multireference coupled cluster theory
journal, May 2012

  • Hanauer, Matthias; Köhn, Andreas
  • The Journal of Chemical Physics, Vol. 136, Issue 20
  • DOI: 10.1063/1.4718700

Theoretical investigation of ground and excited states of the methylene amidogene radical (H2CN)
journal, April 2004

  • Eisfeld, Wolfgang
  • The Journal of Chemical Physics, Vol. 120, Issue 13
  • DOI: 10.1063/1.1650308

Theoretical studies of the reactions of HCN with atomic hydrogen
journal, March 1985

  • Bair, Raymond A.; Dunning, Thom. H.
  • The Journal of Chemical Physics, Vol. 82, Issue 5
  • DOI: 10.1063/1.448323

Dissociation Energy and Ionization Potential of Molecular Hydrogen
journal, November 1969


Formation of nitrogenated organic aerosols in the Titan upper atmosphere
journal, July 2010

  • Imanaka, Hiroshi; Smith, Mark A.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 28
  • DOI: 10.1073/pnas.0913353107

Coupled-cluster characterization of the ground and excited states of the CH2N and CH2P radicals
journal, February 2001

  • Brinkmann, Nicole R.; Wesolowski, Steven S.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 114, Issue 7
  • DOI: 10.1063/1.1337062

Photoelectron spectroscopy of CH 2 N
journal, March 1991

  • Cowles, Daniel C.; Travers, Michael J.; Frueh, Jennifer L.
  • The Journal of Chemical Physics, Vol. 94, Issue 5
  • DOI: 10.1063/1.459773

An efficient linear-scaling CCSD(T) method based on local natural orbitals
journal, September 2013

  • Rolik, Zoltán; Szegedy, Lóránt; Ladjánszki, István
  • The Journal of Chemical Physics, Vol. 139, Issue 9
  • DOI: 10.1063/1.4819401

Toward subchemical accuracy in computational thermochemistry: Focal point analysis of the heat of formation of NCO and [H,N,C,O] isomers
journal, June 2004

  • Schuurman, Michael S.; Muir, Steven R.; Allen, Wesley D.
  • The Journal of Chemical Physics, Vol. 120, Issue 24
  • DOI: 10.1063/1.1707013

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.