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Title: A chemical dynamics study on the gas-phase formation of triplet and singlet C 5 H 2 carbenes

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [1];  [2]; ORCiD logo [1];  [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Department of Chemistry, University of Hawai’i at Manoa, Honolulu, HI 96822,
  2. Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199,, Laboratory of Combustion Physics and Chemistry, Samara National Research University, Samara 443086, Russia,
  3. Institute of Organic Chemistry, Justus Liebig University, 35392 Giessen, Germany
  4. Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199,
+ Show Author Affiliations

Since the postulation of carbenes by Buchner (1903) and Staudinger (1912) as electron-deficient transient species carrying a divalent carbon atom, carbenes have emerged as key reactive intermediates in organic synthesis and in molecular mass growth processes leading eventually to carbonaceous nanostructures in the interstellar medium and in combustion systems. Contemplating the short lifetimes of these transient molecules and their tendency for dimerization, free carbenes represent one of the foremost obscured classes of organic reactive intermediates. Here, we afford an exceptional glance into the fundamentally unknown gas-phase chemistry of preparing two prototype carbenes with distinct multiplicities—triplet pentadiynylidene (HCCCCCH) and singlet ethynylcyclopropenylidene (c-C5H2) carbene—via the elementary reaction of the simplest organic radical—methylidyne (CH)—with diacetylene (HCCCCH) under single-collision conditions. Our combination of crossed molecular beam data with electronic structure calculations and quasi-classical trajectory simulations reveals fundamental reaction mechanisms and facilitates an intimate understanding of bond-breaking processes and isomerization processes of highly reactive hydrocarbon intermediates. Additionally, the agreement between experimental chemical dynamics studies under single-collision conditions and the outcome of trajectory simulations discloses that molecular beam studies merged with dynamics simulations have advanced to such a level that polyatomic reactions with relevance to extreme astrochemical and combustion chemistry conditions can be elucidated at the molecular level and expanded to higher-order homolog carbenes such as butadiynylcyclopropenylidene and triplet heptatriynylidene, thus offering a versatile strategy to explore the exotic chemistry of novel higher-order carbenes in the gas phase.

Research Organization:
Univ. of Hawaii, Honolulu, HI (United States); Florida International Univ. (FIU), Miami, FL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
FG02-03ER15411; FG02-04ER15570
OSTI ID:
1716525
Alternate ID(s):
OSTI ID: 1849429
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 117 Journal Issue: 48; ISSN 0027-8424
Publisher:
Proceedings of the National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English

References (65)

A study of benzene formation in a laminar flow reactor journal January 2002
Reactive Carbon-Chain Molecules:  Synthesis of 1-Diazo-2,4-pentadiyne and Spectroscopic Characterization of Triplet Pentadiynylidene (H−C⋮C−C̈−C⋮C−H) journal March 2006
Electronic spectra of linear HC 5 H and cumulene carbene H 2 C 5 journal June 2015
A mathematical procedure for superimposing atomic coordinates of proteins journal November 1972
Gas-Phase Syntheses of Three Isomeric C 5 H 2 Radical Anions and Their Elusive Neutrals. A Joint Experimental and Theoretical Study journal November 1998
Untangling the chemical evolution of Titan's atmosphere and surface–from homogeneous to heterogeneous chemistry journal January 2010
A solution for the best rotation to relate two sets of vectors journal September 1976
Semiempirical hybrid density functional with perturbative second-order correlation journal January 2006
Accurate equilibrium structures for small polyatomic molecules, radicals and carbenes journal May 2005
Photodissociation of small carbonaceous molecules of astrophysical interest journal January 2008
A simple and efficient CCSD(T)-F12 approximation journal December 2007
AB Initio Geometries for C 2n+1H, C 2n+1H +, and C 2n+1H 2 Species for N = 1,2,3 journal October 1988
Benchmark calculations with correlated molecular wave functions. IV. The classical barrier height of the H+H 2 →H 2 +H reaction journal May 1994
Reduced bond length alternation and helical molecular orbitals in donor and acceptor substituted linear carbon chains journal December 2018
Pentadiynylidene and Its Methyl-Substituted Derivates: Threshold Photoelectron Spectroscopy of R 1 -C 5 -R 2 Triplet Carbon Chains journal February 2019
Elucidating the Chemical Dynamics of the Elementary Reactions of the 1-Propynyl Radical (CH 3 CC; X 2 A 1 ) with Methylacetylene (H 3 CCCH; X 1 A 1 ) and Allene (H 2 CCCH 2 ; X 1 A 1 ) journal June 2019
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Determination of Ensemble-Average Pairwise Root Mean-Square Deviation from Experimental B-Factors journal March 2010
Astronomical detection of H2CCC journal February 1991
Exchange reactions of alkali atoms with alkali halides: a collision complex mechanism journal January 1967
Crossed beam study of the atom-radical reaction of ground state carbon atoms (C( 3 P)) with the vinyl radical (C 2 H 3 (X 2 A′)) journal January 2012
Molecular Reaction Dynamics book January 2005
A crossed molecular beam study on the reaction of methylidyne radicals [CH(X 2 Π)] with acetylene [C 2 H 2 (X 1 Σ g + )]—competing C 3 H 2 + H and C 3 H + H 2 channels journal January 2011
Carbon-13 Isotopic Species of H2C3, H2C4, and H2C5: High-Resolution Rotational Spectra journal February 2002
Structures, Automerizations, and Isomerizations of C 3 H 2 Isomers journal June 1997
Exploring old and new benzene formation pathways in low-pressure premixed flames of aliphatic fuels journal January 2000
Structure of Triplet Propynylidene journal January 1995
The syntheses of C6CH2.− and the corresponding carbenoid cumulene C6CH2 in the gas phase journal January 1998
Detection and Characterization of the Cumulene Carbenes H2C5 and H2C6 journal January 1997
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
Chemical dynamics of the CH(X 2 Π) + C 2 H 4 (X 1 A 1g ), CH(X 2 Π) + C 2 D 4 (X 1 A 1g ), and CD(X 2 Π) + C 2 H 4 (X 1 A 1g ) reactions studied under single collision conditions journal January 2012
Cyclopropenylidene journal August 1984
Laboratory and astronomical identification of cyclopropenylidene, C3H2 journal December 1985
Laboratory detection of propadienylidene, H2CCC journal November 1990
Laboratory Detection of Two New C[TINF]5[/TINF]H[TINF]2[/TINF] Isomers journal December 1998
Simplified CCSD(T)-F12 methods: Theory and benchmarks journal February 2009
A Direct Dynamics Trajectory Study of F - + CH 3 OOH Reactive Collisions Reveals a Major Non-IRC Reaction Path journal August 2007
Effect of the damping function in dispersion corrected density functional theory journal March 2011
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Theoretical Studies of Two Key Low-Lying Carbenes of C 5 H 2 Missing in the Laboratory journal July 2019
Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients journal August 2011
[ITAL]Infrared Space Observatory's[/ITAL] Discovery of C[TINF]4[/TINF]H[TINF]2[/TINF], C[TINF]6[/TINF]H[TINF]2[/TINF], and Benzene in CRL 618 journal January 2001
Vectorization of the general Monte Carlo classical trajectory program VENUS journal October 1991
Cavity ringdown spectroscopy of the linear carbon chains HC7H, HC9H, HC11H, and HC13H journal June 2000
Photodissociation of benzene under collision-free conditions: An ab initio /Rice–Ramsperger–Kassel–Marcus study journal April 2004
Formation of the 1,3,5-Hexatriynyl Radical (C 6 H(X 2 Π)) via the Crossed Beams Reaction of Dicarbon (C 2 (X 1 Σ g + /a 3 Π u )), with Diacetylene (C 4 H 2 (X 1 Σ g + )) journal February 2009
Reaction mechanism and product branching ratios of the CH + C 3 H 4 reactions: a theoretical study journal January 2017
The VENUS/NWChem software package. Tight coupling between chemical dynamics simulations and electronic structure theory journal March 2014
Laser Spectroscopy of the Carbon Chains HC[TINF]7[/TINF]H and HC[TINF]9[/TINF]H journal September 1999
Theoretical Study on the Mechanism of the Dissociation of Benzene. The C 5 H 3 + CH 3 Product Channel journal September 1997
Automerizations and Isomerizations in Propynylidene(HCCCH), Propadienylidene(H2CCC), and Cyclopropenylidene(c-C3H2) journal October 1995
Photodissociation Dynamics of Propyne and Allene:  A View from ab Initio Calculations of the C 3 H n ( n = 1−4) Species and the Isomerization Mechanism for C 3 H 2 journal June 1998
Eight New Carbon Chain Molecules journal November 1997
Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar journal February 2008
Laboratory Detection of Four New Cumulene Carbenes: H 2 C 7 , H 2 C 8 , H 2 C 9 , and D 2 C 10 journal February 2000
Suggestions for an interstellar C 5 H 2 search journal July 2004
Structures and Stabilities of C 5 H 2 Isomers:  Quantum Chemical Studies journal November 1997
Ab initio predictions on the rotational spectra of carbon-chain carbene molecules journal December 1992
Propargylene journal September 1994
Prediction of Reaction Barriers and Thermochemical Properties with Explicitly Correlated Coupled-Cluster Methods: A Basis Set Assessment journal August 2012
Deviations from Born–Oppenheimer Theory in Structural Chemistry: Jahn–Teller, Pseudo Jahn–Teller, and Hidden Pseudo Jahn–Teller Effects in C 3 H 3 and C 3 H 3 – journal August 2013
Laboratory Detection of the Ring-Chain Molecule C[TINF]7[/TINF]H[TINF]2[/TINF] journal July 1997
Laboratory Detection of the Ring-Chain Molecule C[TINF]5[/TINF]H[TINF]2[/TINF] journal July 1997
Vinylidene carbene: a new C3H2 species journal August 1987
Efficient and Accurate Double-Hybrid-Meta-GGA Density Functionals—Evaluation with the Extended GMTKN30 Database for General Main Group Thermochemistry, Kinetics, and Noncovalent Interactions journal December 2010

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Science & Technology - Other Topics
reaction dynamics
molecular beams
trajectory calculations
electronic structure theory
carbenes