Imaging covalent bond formation by H atom scattering from graphene

Jiang, Hongyan; Kammler, Marvin; Ding, Feizhi; Dorenkamp, Yvonne; Manby, Frederick R.; Wodtke, Alec. M.; Miller, III, Thomas F.; Kandratsenka, Alexander; Bünermann, Oliver

doi:10.1126/science.aaw6378

Title: Imaging covalent bond formation by H atom scattering from graphene

Journal Article · Thu Apr 25 00:00:00 EDT 2019 · Science

DOI:https://doi.org/10.1126/science.aaw6378· OSTI ID:1547466

; Kammler, Marvin; Ding, Feizhi;

;

Viewing the atomic-scale motion and energy dissipation pathways involved in forming a covalent bond is a longstanding challenge for chemistry. We performed scattering experiments of H atoms from graphene and observed a bimodal translational energy loss distribution. Using accurate first-principles dynamics simulations, we show that the quasi-elastic channel involves scattering through the physisorption well where collision sites are near the centers of the six-membered C-rings. The second channel results from transient C–H bond formation, where H atoms lose 1 to 2 electron volts of energy within a 10-femtosecond interaction time. This remarkably rapid form of intramolecular vibrational relaxation results from the C atom’s rehybridization during bond formation and is responsible for an unexpectedly high sticking probability of H on graphene.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0004993; DEFOA-0001912

OSTI ID:: 1547466

Journal Information:: Science, Journal Name: Science Vol. 364 Journal Issue: 6438; ISSN 0036-8075

Publisher:: American Association for the Advancement of Science (AAAS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 63 works

Citation information provided by
Web of Science

References (61)

The sticking of H and D atoms on a graphite (0001) surface: The effects of coverage and energy dissipation Kerwin, Jay; Jackson, Bret The Journal of Chemical Physics, Vol. 128, Issue 8 https://doi.org/10.1063/1.2868771	journal	February 2008
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Cohesion energetics of carbon allotropes: Quantum Monte Carlo study Shin, Hyeondeok; Kang, Sinabro; Koo, Jahyun The Journal of Chemical Physics, Vol. 140, Issue 11 https://doi.org/10.1063/1.4867544	journal	March 2014
Embedded Mean-Field Theory Fornace, Mark E.; Lee, Joonho; Miyamoto, Kaito Journal of Chemical Theory and Computation, Vol. 11, Issue 2 https://doi.org/10.1021/ct5011032	journal	January 2015
Quantum dynamics of hydrogen atoms on graphene. II. Sticking Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H. The Journal of Chemical Physics, Vol. 143, Issue 12 https://doi.org/10.1063/1.4931117	journal	September 2015
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Graphene on metal surfaces and its hydrogen adsorption: A meta-GGA functional study Andersen, Mie; Hornekær, Liv; Hammer, Bjørk Physical Review B, Vol. 86, Issue 8 https://doi.org/10.1103/PhysRevB.86.085405	journal	August 2012
Interfacial energy exchange and reaction dynamics in collisions of gases on model organic surfaces Lu, Jessica W.; Day, B. Scott; Fiegland, Larry R. Progress in Surface Science, Vol. 87, Issue 9-12 https://doi.org/10.1016/j.progsurf.2012.07.002	journal	September 2012
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
Extremely short-lived reaction resonances in Cl + HD ( v = 1) → DCl + H due to chemical bond softening Yang, Tiangang; Chen, Jun; Huang, Long Science, Vol. 347, Issue 6217 https://doi.org/10.1126/science.1260527	journal	January 2015
Empirical chemical pseudopotential theory of molecular and metallic bonding Abell, G. C. Physical Review B, Vol. 31, Issue 10 https://doi.org/10.1103/PhysRevB.31.6184	journal	May 1985
ONIOM: A Multilayered Integrated MO + MM Method for Geometry Optimizations and Single Point Energy Predictions. A Test for Diels−Alder Reactions and Pt(P( t -Bu) ₃ ) ₂ + H ₂ Oxidative Addition Svensson, Mats; Humbel, Stéphane; Froese, Robert D. J. The Journal of Physical Chemistry, Vol. 100, Issue 50 https://doi.org/10.1021/jp962071j	journal	January 1996
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
D ECODING THE D YNAMICAL I NFORMATION E MBEDDED IN H IGHLY M IXED Q UANTUM S TATES Keske, John C.; Pate, Brooks H. Annual Review of Physical Chemistry, Vol. 51, Issue 1 https://doi.org/10.1146/annurev.physchem.51.1.323	journal	October 2000
Molecular vibrational energy flow: Beyond the Golden Rule Gruebele, M.; Bigwood, R. International Reviews in Physical Chemistry, Vol. 17, Issue 2 https://doi.org/10.1080/014423598230117	journal	April 1998
Bandgap opening in graphene induced by patterned hydrogen adsorption Balog, Richard; Jørgensen, Bjarke; Nilsson, Louis Nature Materials, Vol. 9, Issue 4 https://doi.org/10.1038/nmat2710	journal	March 2010
Direct picosecond time resolution of dissipative intramolecular vibrational-energy redistribution (IVR) in isolated molecules Felker, Peter M.; Zewail, Ahmed H. Chemical Physics Letters, Vol. 108, Issue 4 https://doi.org/10.1016/0009-2614(84)85196-9	journal	July 1984
An accurate full-dimensional potential energy surface for H–Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption Janke, Svenja M.; Auerbach, Daniel J.; Wodtke, Alec M. The Journal of Chemical Physics, Vol. 143, Issue 12 https://doi.org/10.1063/1.4931669	journal	September 2015
Hydrogen-storage materials for mobile applications Schlapbach, Louis; Züttel, Andreas Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104634	journal	November 2001
Embedded Mean-Field Theory with Block-Orthogonalized Partitioning Ding, Feizhi; Manby, Frederick R.; Miller, Thomas F. Journal of Chemical Theory and Computation, Vol. 13, Issue 4 https://doi.org/10.1021/acs.jctc.6b01065	journal	March 2017
Ring-Polymer Molecular Dynamics: Quantum Effects in Chemical Dynamics from Classical Trajectories in an Extended Phase Space Habershon, Scott; Manolopoulos, David E.; Markland, Thomas E. Annual Review of Physical Chemistry, Vol. 64, Issue 1 https://doi.org/10.1146/annurev-physchem-040412-110122	journal	April 2013
Creation and Disposal of Vibration Energy in Polyatomic Molecules McDonald, J. D. Annual Review of Physical Chemistry, Vol. 30, Issue 1 https://doi.org/10.1146/annurev.pc.30.100179.000333	journal	October 1979
Fast Hartree–Fock theory using local density fitting approximations Polly, Robert; Werner *, Hans-Joachim; Manby, Frederick R. Molecular Physics, Vol. 102, Issue 21-22 https://doi.org/10.1080/0026897042000274801	journal	November 2004
Electron-hole pair excitation determines the mechanism of hydrogen atom adsorption Bunermann, O.; Jiang, H.; Dorenkamp, Y. Science, Vol. 350, Issue 6266 https://doi.org/10.1126/science.aad4972	journal	November 2015
New empirical approach for the structure and energy of covalent systems Tersoff, J. Physical Review B, Vol. 37, Issue 12 https://doi.org/10.1103/PhysRevB.37.6991	journal	April 1988
Transition State Resonances in the Reaction Cl + H ₂ → HCl + H Srinivasan, Jay; Allison, Thomas C.; Schwenke, David W. The Journal of Physical Chemistry A, Vol. 103, Issue 11 https://doi.org/10.1021/jp984549k	journal	March 1999
Non-equilibrium dynamics from RPMD and CMD Welsch, Ralph; Song, Kai; Shi, Qiang The Journal of Chemical Physics, Vol. 145, Issue 20 https://doi.org/10.1063/1.4967958	journal	November 2016
Coupled Cluster and Density Functional Theory Calculations of Atomic Hydrogen Chemisorption on Pyrene and Coronene as Model Systems for Graphene Hydrogenation Wang, Ying; Qian, Hu-Jun; Morokuma, Keiji The Journal of Physical Chemistry A, Vol. 116, Issue 26 https://doi.org/10.1021/jp3023666	journal	June 2012
Molecular dynamics simulations at constant pressure and/or temperature Andersen, Hans C. The Journal of Chemical Physics, Vol. 72, Issue 4 https://doi.org/10.1063/1.439486	journal	February 1980
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Ultimate strength, ripples, sound velocities, and density of phonon states of strained graphene Dmitriev, Sergey V.; Baimova, Julia A.; Savin, Alexander V. Computational Materials Science, Vol. 53, Issue 1 https://doi.org/10.1016/j.commatsci.2011.08.019	journal	February 2012
Understanding adsorption of hydrogen atoms on graphene Casolo, Simone; Løvvik, Ole Martin; Martinazzo, Rocco The Journal of Chemical Physics, Vol. 130, Issue 5 https://doi.org/10.1063/1.3072333	journal	February 2009
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals Hehre, W. J.; Stewart, R. F.; Pople, J. A. The Journal of Chemical Physics, Vol. 51, Issue 6 https://doi.org/10.1063/1.1672392	journal	September 1969
A fully direct RI-HF algorithm: Implementation, optimised auxiliary basis sets, demonstration of accuracy and efficiency Weigend, Florian Physical Chemistry Chemical Physics, Vol. 4, Issue 18 https://doi.org/10.1039/b204199p	journal	August 2002
An ultrahigh vacuum apparatus for H atom scattering from surfaces Bünermann, Oliver; Jiang, Hongyan; Dorenkamp, Yvonne Review of Scientific Instruments, Vol. 89, Issue 9 https://doi.org/10.1063/1.5047674	journal	September 2018
Study of the sticking of a hydrogen atom on a graphite surface using a mixed classical-quantum dynamics method Morisset, S.; Ferro, Y.; Allouche, A. The Journal of Chemical Physics, Vol. 133, Issue 4 https://doi.org/10.1063/1.3463001	journal	July 2010
Structural Relaxation Made Simple Bitzek, Erik; Koskinen, Pekka; Gähler, Franz Physical Review Letters, Vol. 97, Issue 17 https://doi.org/10.1103/PhysRevLett.97.170201	journal	October 2006
Ab initio molecular dynamics for liquid metals Kresse, G. Journal of Non-Crystalline Solids, Vol. 192-193 https://doi.org/10.1016/0022-3093(95)00355-X	journal	December 1995
Clustering of Chemisorbed H(D) Atoms on the Graphite (0001) Surface due to Preferential Sticking Hornekær, L.; Rauls, E.; Xu, W. Physical Review Letters, Vol. 97, Issue 18 https://doi.org/10.1103/PhysRevLett.97.186102	journal	October 2006
Quantum statistics and classical mechanics: Real time correlation functions from ring polymer molecular dynamics Craig, Ian R.; Manolopoulos, David E. The Journal of Chemical Physics, Vol. 121, Issue 8 https://doi.org/10.1063/1.1777575	journal	August 2004
Crossed Molecular Beam Study of F+C2H4, C ₂ D ₄ Parson, J. M.; Lee, Y. T. The Journal of Chemical Physics, Vol. 56, Issue 9 https://doi.org/10.1063/1.1677917	journal	May 1972
Importance of Surface Morphology in Interstellar H2 Formation Hornekaer, L. Science, Vol. 302, Issue 5652 https://doi.org/10.1126/science.1090820	journal	December 2003
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Vibrational Energy Flow in Highly Excited Molecules: Role of Intramolecular Vibrational Redistribution Nesbitt, David J.; Field, Robert W. The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp960698w	journal	January 1996
Local-density-functional study of the fullerenes, graphene and graphite Dunlap, B. I.; Boettger, J. C. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 29, Issue 21 https://doi.org/10.1088/0953-4075/29/21/004	journal	November 1996
Quantum modelling of hydrogen chemisorption on graphene and graphite Karlický, František; Lepetit, Bruno; Lemoine, Didier The Journal of Chemical Physics, Vol. 140, Issue 12 https://doi.org/10.1063/1.4867995	journal	March 2014
Efficient stochastic thermostatting of path integral molecular dynamics Ceriotti, Michele; Parrinello, Michele; Markland, Thomas E. The Journal of Chemical Physics, Vol. 133, Issue 12 https://doi.org/10.1063/1.3489925	journal	September 2010
Intramolecular energy relaxation. Nonrandom decomposition of hexafluorobicyclopropyl Rabinovitch, B. S.; Rynbrandt, J. D. The Journal of Physical Chemistry, Vol. 75, Issue 14 https://doi.org/10.1021/j100683a017	journal	July 1971
Theoretical study of intramolecular vibrational relaxation of acetylenic CH vibration for v =1 and 2 in large polyatomic molecules (CX ₃ ) ₃ YCCH, where X=H or D and Y=C or Si Stuchebrukhov, A. A.; Marcus, R. A. The Journal of Chemical Physics, Vol. 98, Issue 8 https://doi.org/10.1063/1.464843	journal	April 1993
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
Hydrogen vibrational modes on graphene and relaxation of the C–H stretch excitation from first-principles calculations Sakong, Sung; Kratzer, Peter The Journal of Chemical Physics, Vol. 133, Issue 5 https://doi.org/10.1063/1.3474806	journal	August 2010
When sticking influences H ₂ formation Cazaux, S.; Morisset, S.; Spaans, M. Astronomy & Astrophysics, Vol. 535 https://doi.org/10.1051/0004-6361/201117220	journal	October 2011
Is there <mml:math altimg="si1.gif" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:msup><mml:mrow><mml:mi mathvariant="italic">sp</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math>-bound H on epitaxial graphene? Evidence for adsorption on both sides of the sheet Kim, Hyunil; Balgar, Thorsten; Hasselbrink, Eckart Chemical Physics Letters, Vol. 546 https://doi.org/10.1016/j.cplett.2012.07.049	journal	September 2012
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Linear-Response Time-Dependent Embedded Mean-Field Theory Ding, Feizhi; Tsuchiya, Takashi; Manby, Frederick R. Journal of Chemical Theory and Computation, Vol. 13, Issue 9 https://doi.org/10.1021/acs.jctc.7b00666	journal	August 2017
Isotopic effect on the vibrational lifetime of the carbon-deuterium stretch excitation on graphene Sakong, Sung; Kratzer, Peter The Journal of Chemical Physics, Vol. 135, Issue 11 https://doi.org/10.1063/1.3637040	journal	September 2011
A second-generation reactive empirical bond order (REBO) potential energy expression for hydrocarbons Brenner, Donald W.; Shenderova, Olga A.; Harrison, Judith A. Journal of Physics: Condensed Matter, Vol. 14, Issue 4 https://doi.org/10.1088/0953-8984/14/4/312	journal	January 2002

Similar Records

Imaging covalent bond formation by H atom scattering from graphene

Journal Article · Thu Apr 25 00:00:00 EDT 2019 · Science · OSTI ID:1547466

Jiang, Hongyan; Kammler, Marvin; Ding, Feizhi; +6 more

Electrochemically Driven Covalent Functionalization of Graphene from Fluorinated Aryl Iodonium Salts

Journal Article · Fri May 31 00:00:00 EDT 2013 · Journal of Physical Chemistry. C · OSTI ID:1547466

Chan, Calvin K.; Beechem, Thomas E.; Ohta, Taisuke; +3 more

From classical to quantum dynamics of atomic and ionic species interacting with graphene and its analogue

Book · Sun May 01 00:00:00 EDT 2022 · OSTI ID:1547466

Garashchuk, Sofiya V.; Huang, Jingsong; Sumpter, Bobby; +1 more

Title: Imaging covalent bond formation by H atom scattering from graphene

Citation Formats

References (61)

Similar Records

Related Subjects