Dynamics of HCN, HNC, and HNCO Formation in the 193 nm Photodissociation of Formamide

Caster, Kacee L.; Seifert, Nathan A.; Ruscic, Branko; Jasper, Ahren W.; Prozument, Kirill

doi:10.1021/acs.jpca.4c02232

Dynamics of HCN, HNC, and HNCO Formation in the 193 nm Photodissociation of Formamide

Journal Article · Tue Sep 03 00:00:00 EDT 2024 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.4c02232· OSTI ID:2568019

^[1]; Seifert, Nathan A. ^[2]; ^[1]; ^[1]; ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States); University of New Haven, West Haven, CT (United States)

Formamide (NH₂CHO) is the simplest molecule containing a peptide linkage [-NH-C($$=$$O)-], and it plays an essential role in the study of prebiotic chemistry. Exposure to UV irradiation allows formamide to decompose and act as a prebiotic feedstock in the formation of nucleobases and other necessary starting materials. The photodissociation mechanism of gaseous formamide at 193 nm is studied using (a) chirped-pulse Fourier transform millimeter-wave spectroscopy in the 260-290 GHz spectral region in a room-temperature flow-tube reactor at 1 mu bar pressure, (b) a combination of electronic structure theory, transition state theory, and quasiclassical trajectories, and (c) the Active Thermochemical Tables. The HCN and HNC photoproducts of hydrogenated (NH₂CHO) and deuterated (NH₂CDO and ND₂CHO) formamide precursors are examined to gain insight into the photodissociation mechanism. Here, the theoretical investigation has characterized the main pathway leading to each of the HCN/HNC isomers from the precursor isotopologues. The theoretical branching ratio [HNC]/[HCN] = 2.1 for nascent photofragments agrees with the experiment. The effect of the postphotolysis HNC ↔ HCN isomerization on the [HNC]/[HCN] ratio is predicted. We report the experimental branching ratio [HNCO]: ([HNC] + [HCN]) = 12 ± 3 and propose that most of HNCO originates from dissociation on the S-1 electronic state of formamide.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2568019

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 37 Vol. 128; ISSN 1089-5639; ISSN 1520-5215

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Pure Rotational Spectrum of HCN in the Terahertz Region: Use of a New Planar Schottky Diode Multiplier Maiwald, F.; Lewen, F.; Ahrens, V. Journal of Molecular Spectroscopy, Vol. 202, Issue 1 https://doi.org/10.1006/jmsp.2000.8118	journal	July 2000
Reactive Scattering Cross Sections III: Quasiclassical and Semiclassical Methods Truhlar, Donald G.; Muckerman, James T. Atom - Molecule Collision Theory https://doi.org/10.1007/978-1-4613-2913-8_16	book	January 1979
Water-assisted isomerization of the [H, C, N, O] system Cao, Jia; Wang, Zhi Xiang; Gao, Lou Jun Journal of Molecular Modeling, Vol. 21, Issue 3 https://doi.org/10.1007/s00894-015-2628-y	journal	March 2015
Ab initio molecular orbital study of the mechanism of photodissociation of formamide Liu, Dan; Fang, Wei-Hai; Fu, Xiao-Yuan Chemical Physics Letters, Vol. 318, Issue 4-5 https://doi.org/10.1016/S0009-2614(00)00021-X	journal	February 2000
Photodissociation of formamide at 205 nm: The H atom channels Kang, Tae Yeon; Kim, Hong Lae Chemical Physics Letters, Vol. 431, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.09.050	journal	November 2006
Pseudo-equilibrium geometry of HNO determined by an E-Band CP-FTmmW spectrometer Zaleski, Daniel P.; Prozument, Kirill Chemical Physics Letters, Vol. 680 https://doi.org/10.1016/j.cplett.2017.05.040	journal	July 2017
The Cologne Database for Molecular Spectroscopy, CDMS, in the Virtual Atomic and Molecular Data Centre, VAMDC Endres, Christian P.; Schlemmer, Stephan; Schilke, Peter Journal of Molecular Spectroscopy, Vol. 327 https://doi.org/10.1016/j.jms.2016.03.005	journal	September 2016
PGOPHER: A program for simulating rotational, vibrational and electronic spectra Western, Colin M. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 186 https://doi.org/10.1016/j.jqsrt.2016.04.010	journal	January 2017
Formamide and the origin of life Saladino, Raffaele; Crestini, Claudia; Pino, Samanta Physics of Life Reviews, Vol. 9, Issue 1 https://doi.org/10.1016/j.plrev.2011.12.002	journal	March 2012
New physical insights: Formamide discharge decomposition and the role of fragments in the formation of large biomolecules Pastorek, Adam; Clark, Victoria H. J.; Yurchenko, Sergei N. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 278 https://doi.org/10.1016/j.saa.2022.121322	journal	October 2022
A Global Scale Scenario for Prebiotic Chemistry: Silica-Based Self-Assembled Mineral Structures and Formamide Saladino, Raffaele; Botta, Giorgia; Bizzarri, Bruno Mattia Biochemistry, Vol. 55, Issue 19 https://doi.org/10.1021/acs.biochem.6b00255	journal	May 2016
Introduction: Chemical Evolution and the Origins of Life Krishnamurthy, Ramanarayanan; Hud, Nicholas V. Chemical Reviews, Vol. 120, Issue 11 https://doi.org/10.1021/acs.chemrev.0c00409	journal	June 2020
On the HCN – HNC Energy Difference Nguyen, Thanh L.; Baraban, Joshua H.; Ruscic, Branko The Journal of Physical Chemistry A, Vol. 119, Issue 44 https://doi.org/10.1021/acs.jpca.5b08406	journal	October 2015
Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J. The Journal of Physical Chemistry Letters, Vol. 8, Issue 24 https://doi.org/10.1021/acs.jpclett.7b02864	journal	December 2017
Electron-Induced Synthesis of Formamide in Condensed Mixtures of Carbon Monoxide and Ammonia Bredehöft, Jan H.; Böhler, Esther; Schmidt, Fabian ACS Earth and Space Chemistry, Vol. 1, Issue 1 https://doi.org/10.1021/acsearthspacechem.6b00011	journal	February 2017
Can Formamide Be Formed on Interstellar Ice? An Atomistic Perspective Rimola, Albert; Skouteris, Dimitrios; Balucani, Nadia ACS Earth and Space Chemistry, Vol. 2, Issue 7 https://doi.org/10.1021/acsearthspacechem.7b00156	journal	June 2018
Thermal decomposition of formamide: shock tube experiments and ab initio calculations Kakumoto, Terumitsu; Saito, Ko; Imamura, Akira The Journal of Physical Chemistry, Vol. 89, Issue 11 https://doi.org/10.1021/j100257a027	journal	May 1985
Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited ^† Ruscic, Branko; Pinzon, Reinhardt E.; Morton, Melita L. The Journal of Physical Chemistry A, Vol. 108, Issue 45 https://doi.org/10.1021/jp047912y	journal	November 2004
Predictive Theory for Hydrogen Atom−Hydrocarbon Radical Association Kinetics Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 109, Issue 21 https://doi.org/10.1021/jp0508608	journal	June 2005
Theoretical Study of Formamide Decomposition Pathways Nguyen, Vinh Son; Abbott, Heather L.; Dawley, M. Michele The Journal of Physical Chemistry A, Vol. 115, Issue 5 https://doi.org/10.1021/jp109143j	journal	January 2011
Ab Initio and RRKM Study of the HCN/HNC Elimination Channels from Vinyl Cyanide Homayoon, Zahra; Vázquez, Saulo A.; Rodríguez-Fernández, Roberto The Journal of Physical Chemistry A, Vol. 115, Issue 6 https://doi.org/10.1021/jp109843a	journal	February 2011
Laser Spark Formamide Decomposition Studied by FT-IR Spectroscopy Ferus, M.; Kubelík, P.; Civiš, S. The Journal of Physical Chemistry A, Vol. 115, Issue 44 https://doi.org/10.1021/jp205413d	journal	October 2011
Decomposition Pathways of the Neutral and Protonated Formamide in Some Lower-Lying Excited States Nguyen, Huyen Thi; Nguyen, Vinh Son; Trung, Nguyen Tien The Journal of Physical Chemistry A, Vol. 117, Issue 33 https://doi.org/10.1021/jp405657y	journal	August 2013
High-Energy Chemistry of Formamide: A Simpler Way for Nucleobase Formation Ferus, Martin; Michalčíková, Regina; Shestivská, Violetta The Journal of Physical Chemistry A, Vol. 118, Issue 4 https://doi.org/10.1021/jp411415p	journal	January 2014
Photoionization Mass Spectrometric Study of the Prebiotic Species Formamide in the 10−20 eV Photon Energy Range Leach, Sydney; Jochims, Hans-Werner; Baumgärtel, Helmut The Journal of Physical Chemistry A, Vol. 114, Issue 14 https://doi.org/10.1021/jp9098182	journal	January 2010
Collisional excitation of HNC by He found to be stronger than for structural isomer HCN in experiments at the low temperatures of interstellar space Hays, Brian M.; Gupta, Divita; Guillaume, Théo Nature Chemistry, Vol. 14, Issue 7 https://doi.org/10.1038/s41557-022-00936-x	journal	May 2022
Estimating the capacity for production of formamide by radioactive minerals on the prebiotic Earth Adam, Zachary R.; Hongo, Yayoi; Cleaves, H. James Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-017-18483-8	journal	January 2018
Chirped-pulse millimeter-wave spectroscopy for dynamics and kinetics studies of pyrolysis reactions Prozument, Kirill; Barratt Park, G.; Shaver, Rachel G. Phys. Chem. Chem. Phys., Vol. 16, Issue 30 https://doi.org/10.1039/C3CP55352C	journal	January 2014
HCN elimination from vinyl cyanide: product energy partitioning, the role of hydrogen–deuterium exchange reactions and a new pathway Vázquez, Saulo A.; Martínez-Núñez, Emilio Physical Chemistry Chemical Physics, Vol. 17, Issue 10 https://doi.org/10.1039/C4CP05626D	journal	January 2015
Prebiotic synthesis of nucleic acids and their building blocks at the atomic level – merging models and mechanisms from advanced computations and experiments Šponer, Judit E.; Szabla, Rafał; Góra, Robert W. Physical Chemistry Chemical Physics, Vol. 18, Issue 30 https://doi.org/10.1039/C6CP00670A	journal	January 2016
Isomer-specific detection in the UV photodissociation of the propargyl radical by chirped-pulse mm-wave spectroscopy in a pulsed quasi-uniform flow Broderick, Bernadette M.; Suas-David, Nicolas; Dias, Nureshan Physical Chemistry Chemical Physics, Vol. 20, Issue 8 https://doi.org/10.1039/C7CP06211G	journal	January 2018
Unimolecular decomposition of formamide via direct chemical dynamics simulations Gahlaut, Anchal; Paranjothy, Manikandan Physical Chemistry Chemical Physics, Vol. 20, Issue 13 https://doi.org/10.1039/C8CP00541A	journal	January 2018
Unimolecular photolysis mechanisms of formamide: the effect of thermal energy Suwannakham, Parichart; Sagarik, Kritsana Physical Chemistry Chemical Physics, Vol. 22, Issue 44 https://doi.org/10.1039/D0CP03718D	journal	January 2020
From gaseous HCN to nucleobases at the cosmic silicate dust surface: an experimental insight into the onset of prebiotic chemistry in space Santalucia, Rosangela; Pazzi, Marco; Bonino, Francesca Physical Chemistry Chemical Physics, Vol. 24, Issue 12 https://doi.org/10.1039/D1CP05407D	journal	January 2022
Photochemistry and free-radical reactions in formamide vapour Boden, J. C.; Back, R. A. Transactions of the Faraday Society, Vol. 66 https://doi.org/10.1039/tf9706600175	journal	January 1970
High-temperature photolysis and the pyrolysis of formamide vapour, and the thermal decomposition of the carbamyl radical Back, R. A.; Boden, J. C. Transactions of the Faraday Society, Vol. 67 https://doi.org/10.1039/tf9716700088	journal	January 1971
HNCO-based synthesis of formamide in planetary atmospheres Ferus, M.; Laitl, V.; Knizek, A. Astronomy & Astrophysics, Vol. 616 https://doi.org/10.1051/0004-6361/201833003	journal	August 2018
Exploring the formation pathways of formamide Allen, V.; van der Tak, F. F. S.; López-Sepulcre, A. Astronomy & Astrophysics, Vol. 636 https://doi.org/10.1051/0004-6361/201935791	journal	April 2020
HCN-to-HNC intensity ratio: a new chemical thermometer for the molecular ISM Hacar, A.; Bosman, A. D.; van Dishoeck, E. F. Astronomy & Astrophysics, Vol. 635 https://doi.org/10.1051/0004-6361/201936516	journal	February 2020
Simulation of the photodeactivation of formamide in the nO-π∗ and π-π∗ states: An ab initio on-the-fly surface-hopping dynamics study Antol, Ivana; Eckert-Maksić, Mirjana; Barbatti, Mario The Journal of Chemical Physics, Vol. 127, Issue 23 https://doi.org/10.1063/1.2804862	journal	December 2007
A bond length reaction coordinate for unimolecular reactions. II. Microcanonical and canonical implementations with application to the dissociation of NCNO Klippenstein, Stephen J. The Journal of Chemical Physics, Vol. 94, Issue 10 https://doi.org/10.1063/1.460276	journal	May 1991
Variational optimizations in the Rice–Ramsperger–Kassel–Marcus theory calculations for unimolecular dissociations with no reverse barrier Klippenstein, Stephen J. The Journal of Chemical Physics, Vol. 96, Issue 1 https://doi.org/10.1063/1.462472	journal	January 1992
Millimeter and submillimeter wave spectroscopy of HNC and DNC in the vibrationally excited states Okabayashi, Toshiaki; Tanimoto, Mitsutoshi The Journal of Chemical Physics, Vol. 99, Issue 5 https://doi.org/10.1063/1.465135	journal	September 1993
Photodissociation transition states characterized by chirped pulse millimeter wave spectroscopy Prozument, Kirill; Baraban, Joshua H.; Changala, P. Bryan Proceedings of the National Academy of Sciences, Vol. 117, Issue 1 https://doi.org/10.1073/pnas.1911326116	journal	December 2019
Quantum calculations of inelastic scattering of HCN and HNC by Ar Bowman, Joel; Padmavathi, D. Annapurna Molecular Physics, Vol. 88, Issue 1 https://doi.org/10.1080/00268979609482398	journal	May 1996
Molecular decompositions of acetaldehyde and formamide: theoretical studies using Hartree-Fock, Moller-Plesset and density functional theories Martell, By JAIME M.; Goddard, HENGTAI YU and JOHN D. Molecular Physics, Vol. 92, Issue 3 https://doi.org/10.1080/002689797170248	journal	October 1997
Microwave Detection of Interstellar Formamide Rubin, R. H.; Swenson, G. W. , Jr.; Benson, R. C. The Astrophysical Journal, Vol. 169 https://doi.org/10.1086/180810	journal	October 1971
Abundances of HCN and HNC in Dark Cloud Cores Hirota, Tomoya; Yamamoto, Satoshi; Mikami, Hitomi The Astrophysical Journal, Vol. 503, Issue 2 https://doi.org/10.1086/306032	journal	August 1998
MECHANISTICAL STUDIES ON THE PRODUCTION OF FORMAMIDE (H ₂ NCHO) WITHIN INTERSTELLAR ICE ANALOGS Jones, Brant M.; Bennett, Christopher J.; Kaiser, Ralf I. The Astrophysical Journal, Vol. 734, Issue 2 https://doi.org/10.1088/0004-637X/734/2/78	journal	May 2011
The Hnc/Hcn Ratio in Star-Forming Regions Graninger, Dawn M.; Herbst, Eric; Öberg, Karin I. The Astrophysical Journal, Vol. 787, Issue 1 https://doi.org/10.1088/0004-637X/787/1/74	journal	May 2014
Active Thermochemical Tables: thermochemistry for the 21st century Ruscic, Branko; Pinzon, Reinhardt E.; Laszewski, Gregor von Journal of Physics: Conference Series, Vol. 16 https://doi.org/10.1088/1742-6596/16/1/078	journal	January 2005
The interstellar gas-phase chemistry of HCN and HNC Loison, Jean-Christophe; Wakelam, Valentine; Hickson, Kevin M. Monthly Notices of the Royal Astronomical Society, Vol. 443, Issue 1 https://doi.org/10.1093/mnras/stu1089	journal	July 2014
Molecules with a peptide link in protostellar shocks: a comprehensive study of L1157 Mendoza, Edgar; Lefloch, B.; López-Sepulcre, A. Monthly Notices of the Royal Astronomical Society, Vol. 445, Issue 1 https://doi.org/10.1093/mnras/stu1718	journal	September 2014
Shedding light on the formation of the pre-biotic molecule formamide with ASAI López-Sepulcre, A.; Jaber, Ali A.; Mendoza, E. Monthly Notices of the Royal Astronomical Society, Vol. 449, Issue 3 https://doi.org/10.1093/mnras/stv377	journal	April 2015
The rotational excitation of HCN and HNC by He: new insights on the HCN/HNC abundance ratio in molecular clouds Sarrasin, E.; Abdallah, D. Ben; Wernli, M. Monthly Notices of the Royal Astronomical Society https://doi.org/10.1111/j.1365-2966.2010.16312.x	journal	February 2010
A Production of Amino Acids Under Possible Primitive Earth Conditions Miller, S. L. Science, Vol. 117, Issue 3046 https://doi.org/10.1126/science.117.3046.528	journal	May 1953
Organic Compound Synthes on the Primitive Eart: Several questions about the origin of life have been answered, but much remains to be studied Miller, S. L.; Urey, H. C. Science, Vol. 130, Issue 3370 https://doi.org/10.1126/science.130.3370.245	journal	July 1959
Spectroscopic characterization of isomerization transition states Baraban, J. H.; Changala, P. B.; Mellau, G. C. Science, Vol. 350, Issue 6266 https://doi.org/10.1126/science.aac9668	journal	December 2015
The Microwave and Millimetre Wave Spectrum, Molecular Constants, Dipole Moment, and Structure of Isocyanic Acid, HNCO Hocking, W. H.; Gerry, M. C. L.; Winnewisser, Gisbert Canadian Journal of Physics, Vol. 53, Issue 19 https://doi.org/10.1139/p75-239	journal	October 1975
Formamide-Based Post-impact Thermal Prebiotic Synthesis in Simulated Craters: Intermediates, Products and Mechanism Ferus, Martin; Knížek, Antonín; Petera, Lukáš Frontiers in Astronomy and Space Sciences, Vol. 9 https://doi.org/10.3389/fspas.2022.882145	journal	May 2022

Similar Records

The Photodissociation of HCN and HNC: Effects on the HNC/HCN Abundance Ratio in the Interstellar Medium

Journal Article · Mon Mar 20 00:00:00 EDT 2017 · Astrophysical Journal · OSTI ID:22661253

New detections of HNC in planetary nebulae: evolution of the [HCN]/[HNC] ratio

Journal Article · Thu Jan 19 23:00:00 EST 2017 · Astrophysical Journal · OSTI ID:22869572

Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route

Journal Article · Tue Dec 13 23:00:00 EST 2011 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1564829

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Dynamics of HCN, HNC, and HNCO Formation in the 193 nm Photodissociation of Formamide

Citation Formats

References (60)

Similar Records

Related Subjects