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

Wiens, Avery E.; Copan, Andreas V.; Rossomme, Elliot C.; Aroeira, Gustavo J. R.; Bernstein, Olivia M.; Agarwal, Jay; Schaefer, Henry F.

doi:10.1063/1.5004984

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

Abstract

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 ofmore »« less

Authors:

Wiens, Avery E. ^[1]; Copan, Andreas V. ^[1];

^[2]; Aroeira, Gustavo J. R. ^[3];

^[4]; Agarwal, Jay ^[1];

^[1]

Univ. of Georgia, Athens, GA (United States)
Univ. of Georgia, Athens, GA (United States); Messiah College, Mechanicsburg, PA (United States)
Univ. of Georgia, Athens, GA (United States); Federal Univ. of Sao Paulo, Sao Paulo (Brazil)
Univ. of Georgia, Athens, GA (United States); Biola Univ., La Mirada, CA (United States)

Publication Date:: Wed Jan 03 00:00:00 EST 2018

Research Org.:: Univ. of Georgia, Athens, GA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

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.

Copy to clipboard


                    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.  https://doi.org/10.1063/1.5004984

Copy to clipboard


                    Wiens, Avery E., Copan, Andreas V., Rossomme, Elliot C., Aroeira, Gustavo J. R., Bernstein, Olivia M., Agarwal, Jay, and Schaefer, Henry F. 2018.  
        "Reinterpreting the infrared spectrum of H + HCN: Methylene amidogen radical and its coproducts".  United States.  https://doi.org/10.1063/1.5004984.  https://www.osti.gov/servlets/purl/1468296.

Copy to clipboard


                    
@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},

  url          = {https://www.osti.gov/biblio/1468296},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 1,

  volume       = 148,

  place        = {United States},

  year         = {Wed Jan 03 00:00:00 EST 2018},

  month        = {Wed Jan 03 00:00:00 EST 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1063/1.5004984

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

Figures / Tables:

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.

All figures and tables (7 total)

Save / Share:

Export Metadata

Save to My Library

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
https://doi.org/10.1021/acs.jctc.7b00174

Analytic energy gradients for the spin-free exact two-component theory using an exact block diagonalization for the one-electron Dirac Hamiltonian
journal, August 2011

Cheng, Lan; Gauss, Jürgen
The Journal of Chemical Physics, Vol. 135, Issue 8
https://doi.org/10.1063/1.3624397

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
https://doi.org/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
https://doi.org/10.1021/acs.jpca.7b01182

The role of accurate quantum mechanical computations in the assignment of vibrational spectra for unstable free radicals: H2CN and F2CN as test cases
journal, January 2009

Puzzarini, Cristina; Barone, Vincenzo
Chemical Physics Letters, Vol. 467, Issue 4-6
https://doi.org/10.1016/j.cplett.2008.11.067

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
https://doi.org/10.1002/wcms.82

The Vibration-Rotation Energies of Molecules
journal, April 1951

Nielsen, Harald H.
Reviews of Modern Physics, Vol. 23, Issue 2
https://doi.org/10.1103/revmodphys.23.90

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

Kaye, Jack A.; Strobel, Darrell F.
Icarus, Vol. 54, Issue 3
https://doi.org/10.1016/0019-1035(83)90238-5

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

Halonen, Lauri; Duxbury, Geoffrey
Chemical Physics Letters, Vol. 118, Issue 3
https://doi.org/10.1016/0009-2614(85)85309-4

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
https://doi.org/10.1063/1.476449

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

Copan, Andreas V.; Schaefer, Henry F.; Agarwal, Jay
Molecular Physics, Vol. 113, Issue 19-20
https://doi.org/10.1080/00268976.2015.1063729

Relativistic Internally Contracted Multireference Electron Correlation Methods
journal, September 2015

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

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

Domcke, W.; Köppel, H.; Cederbaum, L. S.
Molecular Physics, Vol. 43, Issue 4
https://doi.org/10.1080/00268978100101721

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
https://doi.org/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
https://doi.org/10.1063/1.443527

The adiabatic correction to molecular potential surfaces in the SCF approximation
journal, January 1984

Sellers, Harrell; Pulay, Peter
Chemical Physics Letters, Vol. 103, Issue 6
https://doi.org/10.1016/0009-2614(84)85277-x

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
https://doi.org/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
https://doi.org/10.1139/p56-085

A systematic study of molecular vibrational anharmonicity and vibration—rotation interaction by self-consistent-field higher-derivative methods. Asymmetric top molecules
journal, July 1988

Clabo, D. Allen; Allen, Wesley D.; Remington, Richard B.
Chemical Physics, Vol. 123, Issue 2
https://doi.org/10.1016/0301-0104(88)87271-9

Higher excitations in coupled-cluster theory
journal, August 2001

Kállay, Mihály; Surján, Péter R.
The Journal of Chemical Physics, Vol. 115, Issue 7
https://doi.org/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 ₁ ← ² B ₂ Assignment
journal, June 2006

Teslja, Alexey; Dagdigian, Paul J.; Banck, Michael
The Journal of Physical Chemistry A, Vol. 110, Issue 25
https://doi.org/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
https://doi.org/10.1063/1.456153

The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water
journal, May 1993

Feller, David
The Journal of Chemical Physics, Vol. 98, Issue 9
https://doi.org/10.1063/1.464749

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
https://doi.org/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
https://doi.org/10.1039/b102907j

Excited state dynamics of H2CN radicals
journal, November 1999

Bernard, Eugene J.; Strazisar, Brian R.; Davis, H. Floyd
Chemical Physics Letters, Vol. 313, Issue 3-4
https://doi.org/10.1016/s0009-2614(99)01062-3

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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/10.1063/1.1950567

The infrared spectrum of methylenimine
journal, June 1975

Jacox, Marilyn E.; Milligan, Dolphus E.
Journal of Molecular Spectroscopy, Vol. 56, Issue 3
https://doi.org/10.1016/0022-2852(75)90122-8

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
https://doi.org/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
https://doi.org/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
https://doi.org/10.1021/jp022197i

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

Julienne, Paul S.; Krauss, Morris
Journal of Molecular Spectroscopy, Vol. 56, Issue 2
https://doi.org/10.1016/0022-2852(75)90241-6

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

Szalay, Péter G.; Gauss, Jürgen
The Journal of Chemical Physics, Vol. 107, Issue 21
https://doi.org/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
https://doi.org/10.1063/1.450020

Analysis of CH ₂ a ̃ ¹ A ₁ (1,0,0) and (0,0,1) Coriolis‐coupled states, a ̃ ¹ A ₁ – X ̃ ³ B ₁ spin–orbit coupling, and the equilibrium structure of CH ₂ a ̃ ¹ A ₁ state
journal, December 1989

Petek, Hrvoje; Nesbitt, David J.; Darwin, David C.
The Journal of Chemical Physics, Vol. 91, Issue 11
https://doi.org/10.1063/1.457375

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
https://doi.org/10.1063/1.1701294

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

Deegan, Miles J. O.; Knowles, Peter J.
Chemical Physics Letters, Vol. 227, Issue 3
https://doi.org/10.1016/0009-2614(94)00815-9

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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/10.1063/1.466062

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

Schaefer, H. F.
Science, Vol. 231, Issue 4742
https://doi.org/10.1126/science.231.4742.1100

Approximate treatment of higher excitations in coupled-cluster theory. II. Extension to general single-determinant reference functions and improved approaches for the canonical Hartree–Fock case
journal, October 2008

Kállay, Mihály; Gauss, Jürgen
The Journal of Chemical Physics, Vol. 129, Issue 14
https://doi.org/10.1063/1.2988052

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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/10.1086/187362

Chemical Reactions in Energetic Materials
journal, October 1992

Adams, G. F.; Shaw, R. W.
Annual Review of Physical Chemistry, Vol. 43, Issue 1
https://doi.org/10.1146/annurev.pc.43.100192.001523

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
https://doi.org/10.1021/j100311a008

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
https://doi.org/10.1021/j100173a012

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

Jensen, Frank
Chemical Physics Letters, Vol. 169, Issue 6
https://doi.org/10.1016/0009-2614(90)85641-o

The infrared spectrum of thioformaldehyde
journal, September 1971

Johns, J. W. C.; Olson, W. B.
Journal of Molecular Spectroscopy, Vol. 39, Issue 3
https://doi.org/10.1016/0022-2852(71)90219-0

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

Morgan, Cornelius U.; Beyer, Richard A.
Combustion and Flame, Vol. 36
https://doi.org/10.1016/0010-2180(79)90049-x

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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/10.1063/1.448323

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

Herzberg, G.
Physical Review Letters, Vol. 23, Issue 19
https://doi.org/10.1103/physrevlett.23.1081

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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/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
https://doi.org/10.1063/1.1707013

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

Copan, Andreas V.; Schaefer, Henry F.; Agarwal, Jay
Taylor & Francis
https://doi.org/10.6084/m9.figshare.1477836

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

Copan, Andreas V.; Schaefer, Henry F.; Agarwal, Jay
Taylor & Francis
https://doi.org/10.6084/m9.figshare.1477836.v1

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

Copan, Andreas V.; Schaefer, Henry F.; Agarwal, Jay
Taylor & Francis
https://doi.org/10.6084/m9.figshare.1477836.v2

Relativistic Internally Contracted Multireference Electron Correlation Methods
text, January 2015

Shiozaki, Toru; Mizukami, Wataru
arXiv
https://doi.org/10.48550/arxiv.1508.01461

Works referencing / citing this record:

Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H ₂ CN)
journal, September 2018

Abbott, Adam S.; Glick, Zach L.; Schaefer, Henry F.
The Journal of Chemical Physics, Vol. 149, Issue 9
https://doi.org/10.1063/1.5042763

Figures / Tables found in this record:

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

Similar records in OSTI.GOV collections:

Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H₂CN)

Journal Article Abbott, Adam; Glick, Zach; Schaefer, Henry - Journal of Chemical Physics

The odd electronic absorption spectrum of H₂CN has been of great interest to experiment. Herein, this system is reported on extensively by applying theoretical methods to the ground and low-lying excited electronic states. Employing a large breadth of high-level ab initio computations, including coupled cluster [CCSD(T) and CCSDT(Q)] and multireference configuration interaction [MRCISD+Q] methods, we comprehensively demonstrate that the most recent experimental and theoretical interpretations of the electronic spectrum of H₂CN are in error. The previous assignments of the two broad features in the spectrum as the origin 0$$^{0}_{0}$$ (~35 050 cm^–1) and 4$$^{2}_{0}$$ (~35 600 cm^–1)$$\widetilde{B}$$²A₁←$$\widetilde{X}$$²B₂ transitions are bothmore »« less
Cited by 1
https://doi.org/10.1063/1.5042763

Full Text Available
Vibrational autoionization of state-selective jet-cooled methanethiol (CH₃SH) investigated with infrared + vacuum-ultraviolet photoionization

Journal Article Xie, Min; Shen, Zhitao; Pratt, S.; ... - Physical Chemistry Chemical Physics. PCCP (Print)

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. In this work, we employed time-of-flight mass detection of CH₃SH⁺ to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH₃SH) on exciting CH₃SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν₃, SH stretching mode) and 2948 cm^-1 (ν₂, CH₃ symmetric stretching mode) was employed, the Rydbergmore »« less
Cited by 3
https://doi.org/10.1039/C7CP06433K

Full Text Available
Vibrational and electronic spectra of the H + HCN reaction products trapped in solid argon

Journal Article Jacox, M - J. Phys. Chem.; (United States)

The reaction of HCN isolated in solid argon with H atoms formed by photolysis or by a discharge leads to the stabilization of a sufficient concentration of H/sub 2/CN for observation of both its vibrational and electronic absorption spectra. Detailed isotopic substitution experiments have led to a vibrational assignment for this species. The analysis of the vibrational data is consistent with a planar molecular structure and with partial triple bond character for the CN bond. The previously reported electronic absorption of H/sub 2/CH have been reproduced, with only a small matrix shift. The appearance of more highly excited members ofmore »« less
https://doi.org/10.1021/j100311a008
Reduced dimension rovibrational variational calculations of the S₁ state of C₂H₂. II. The S₁ rovibrational manifold and the effects of isomerization

Journal Article Changala, P.; Baraban, Joshua; Stanton, John; ... - Journal of Chemical Physics

Reduced dimension variational calculations have been performed for the rovibrational level structure of the S₁ state of acetylene. The state reflects an unusually complicated level structure, for various reasons. First, the potential energy surface has two accessible conformers, trans and cis. The cis conformer lies about 2700 cm^–1 above the trans, and the barrier to cis-trans isomerization lies about 5000 cm^–1 above the trans minimum. The trans vibrations ν₄ (torsion) and ν₆ (asym. bend) interact very strongly by Darling-Dennison and Coriolis resonances, such that their combination levels and overtones form polyads with unexpected structures. Both conformers exhibit very large x36more »« less
Cited by 8
https://doi.org/10.1063/1.4859876

Full Text Available
Cis-trans isomerization in the S₁ state of acetylene: Identification of cis-well vibrational levels

Journal Article Merer, Anthony; Steeves, Adam; Baraban, Joshua; ... - Journal of Chemical Physics

A systematic analysis of the S1-trans (Ã¹A_u) state of acetylene, using IR-UV double resonance along with one-photon fluorescence excitation spectra, has allowed assignment of at least part of every single vibrational state or polyad up to a vibrational energy of 4200 cm–1. Four observed vibrational levels remain unassigned, for which no place can be found in the level structure of the trans-well. The most prominent of these lies at 46 175 cm^-1. Its ¹³C isotope shift, exceptionally long radiative lifetime, unexpected rotational selection rules, and lack of significant Zeeman effect, combined with the fact that no other singlet electronic statesmore »« less
Cited by 20
https://doi.org/10.1063/1.3599091

Full Text Available

Similar Records

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

Abstract

Citation Formats

Figures / Tables:

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

Analytic energy gradients for the spin-free exact two-component theory using an exact block diagonalization for the one-electron Dirac Hamiltonian journal, August 2011

Nitramine propellant ignition and combustion research journal, January 1991

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

The role of accurate quantum mechanical computations in the assignment of vibrational spectra for unstable free radicals: H2CN and F2CN as test cases journal, January 2009

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

The Vibration-Rotation Energies of Molecules journal, April 1951

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

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

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

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

The adiabatic correction to molecular potential surfaces in the SCF approximation journal, January 1984

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

The Raman Spectrum of Ethylene journal, August 1956

A systematic study of molecular vibrational anharmonicity and vibration—rotation interaction by self-consistent-field higher-derivative methods. Asymmetric top molecules journal, July 1988

Higher excitations in coupled-cluster theory journal, August 2001

Experimental and Theoretical Study of the Electronic Spectrum of the Methylene Amidogen Radical (H 2 CN): Verification of the 2 A 1 ← 2 B 2 Assignment journal, June 2006

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

The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water journal, May 1993

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

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

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

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

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

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

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

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

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

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

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

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

The infrared spectrum of methylenimine journal, June 1975

Configuration interaction calculations on the nitrogen molecule journal, January 1974

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

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

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

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

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

Analysis of CH 2 a ̃ 1 A 1 (1,0,0) and (0,0,1) Coriolis‐coupled states, a ̃ 1 A 1 – X ̃ 3 B 1 spin–orbit coupling, and the equilibrium structure of CH 2 a ̃ 1 A 1 state journal, December 1989

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

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

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

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

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

The heat of formation of NCO journal, September 1993

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

Approximate treatment of higher excitations in coupled-cluster theory. II. Extension to general single-determinant reference functions and improved approaches for the canonical Hartree–Fock case journal, October 2008

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Photoelectron spectroscopy of CH 2 N − journal, March 1991

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

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

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

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

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

Analytic energy gradients for the spin-free exact two-component theory using an exact block diagonalization for the one-electron Dirac Hamiltonian
journal, August 2011

Nitramine propellant ignition and combustion research
journal, January 1991

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

The role of accurate quantum mechanical computations in the assignment of vibrational spectra for unstable free radicals: H2CN and F2CN as test cases
journal, January 2009

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

The Vibration-Rotation Energies of Molecules
journal, April 1951

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

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

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

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

The adiabatic correction to molecular potential surfaces in the SCF approximation
journal, January 1984

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

The Raman Spectrum of Ethylene
journal, August 1956

A systematic study of molecular vibrational anharmonicity and vibration—rotation interaction by self-consistent-field higher-derivative methods. Asymmetric top molecules
journal, July 1988

Higher excitations in coupled-cluster theory
journal, August 2001

Experimental and Theoretical Study of the Electronic Spectrum of the Methylene Amidogen Radical (H ₂ CN): Verification of the ² A ₁ ← ² B ₂ Assignment
journal, June 2006

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

The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water
journal, May 1993

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

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

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

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

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

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

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

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

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

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

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

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

The infrared spectrum of methylenimine
journal, June 1975

Configuration interaction calculations on the nitrogen molecule
journal, January 1974

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

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

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

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

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

Analysis of CH ₂ a ̃ ¹ A ₁ (1,0,0) and (0,0,1) Coriolis‐coupled states, a ̃ ¹ A ₁ – X ̃ ³ B ₁ spin–orbit coupling, and the equilibrium structure of CH ₂ a ̃ ¹ A ₁ state
journal, December 1989

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

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

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

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

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

The heat of formation of NCO
journal, September 1993

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

Approximate treatment of higher excitations in coupled-cluster theory. II. Extension to general single-determinant reference functions and improved approaches for the canonical Hartree–Fock case
journal, October 2008

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Photoelectron spectroscopy of CH ₂ N ⁻
journal, March 1991

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

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

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

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

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

Relativistic Internally Contracted Multireference Electron Correlation Methods
text, January 2015

Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H ₂ CN)
journal, September 2018