Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C 60

Stefanou, M.; Chandler, H. J.; Mignolet, B.; Williams, E.; Nanoh, S. A.; Thompson, J. O. F.; Remacle, F.; Schaub, R.; Campbell, E. E. B.

doi:10.1039/C8NR07088A

Title: Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C ₆₀

Journal Article · Thu Feb 07 00:00:00 EST 2019 · Nanoscale

DOI:https://doi.org/10.1039/C8NR07088A· OSTI ID:1479118

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^[3]; Williams, E. ^[1]; Nanoh, S. A. ^[2]; Thompson, J. O. F. ^[1];

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EaStCHEM and School of Chemistry, University of Edinburgh, Edinburgh, UK
EaStCHEM and School of Chemistry, University of St Andrews, UK
Theoretical Physical Chemistry, Research Unit MOLSYS, University of Liège, B4000 Liège, Belgium
EaStCHEM and School of Chemistry, University of Edinburgh, Edinburgh, UK, Division of Quantum Phases and Devices

Gas phase photoelectron spectroscopy (Rydberg Fingerprint Spectroscopy), TDDFT calculations and low temperature STM studies are combined to provide detailed information on the properties of the diffuse, low-lying Rydberg-like SAMO states of isolated Li@C₆₀ endohedral fullerenes. The presence of the encapsulated Li is shown by the calculations to produce a significant distortion of the lowest-lying S- and P-SAMOs that is dependent on the position of the Li inside the fullerene cage. Under the high temperature conditions of the gas phase experiments, the Li is mobile and able to access different positions within the cage. This is accounted for in the comparison with theory that shows a very good agreement of the photoelectron angular distributions, allowing the symmetry of the observed SAMO states to be identified. When adsorbed on a metal substrate at low temperature, a strong interaction between the low-lying SAMOs and the metal substrate moves these states to energies much closer to the Fermi energy compared to the situation for empty C₆₀ while the Li remains frozen in an off-centre position.

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Research Organization:: Wayne State Univ., Detroit, MI (United States)

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

Grant/Contract Number:: SC0012628

OSTI ID:: 1479118

Alternate ID(s):: OSTI ID: 1611909

Journal Information:: Nanoscale, Journal Name: Nanoscale Vol. 11 Journal Issue: 6; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 14 works

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References (45)

How free are encapsulated atoms in C60? Li, Y. S.; Tománek, D. Chemical Physics Letters, Vol. 221, Issue 5-6 https://doi.org/10.1016/0009-2614(94)00297-5	journal	April 1994
Charge transfer and screening in individual $C_{60}$ molecules on metal substrates: A scanning tunneling spectroscopy and theoretical study Lu, Xinghua; Grobis, M.; Khoo, K. H. Physical Review B, Vol. 70, Issue 11 https://doi.org/10.1103/PhysRevB.70.115418	journal	September 2004
Probing excited electronic states and ionisation mechanisms of fullerenes Johansson, J. Olof; Campbell, Eleanor E. B. Chemical Society Reviews, Vol. 42, Issue 13 https://doi.org/10.1039/c3cs60047e	journal	January 2013
Time-efficient computation of the electronic structure of the C60 super-atom molecular orbital (SAMO) states in TDDFT Mignolet, B.; Remacle, F. INTERNATIONAL CONFERENCE OF COMPUTATIONAL METHODS IN SCIENCES AND ENGINEERING 2016 (ICCMSE 2016), AIP Conference Proceedings https://doi.org/10.1063/1.4968641	conference	January 2016
Angular-resolved Photoelectron Spectroscopy of Superatom Orbitals of Fullerenes Johansson, J. Olof; Henderson, Gordon G.; Remacle, Françoise Physical Review Letters, Vol. 108, Issue 17 https://doi.org/10.1103/PhysRevLett.108.173401	journal	April 2012
Scanning tunneling microscopy studies of $C_{60}$ monolayers on Au(111) Gardener, J. A.; Briggs, G. A. D.; Castell, M. R. Physical Review B, Vol. 80, Issue 23 https://doi.org/10.1103/PhysRevB.80.235434	journal	December 2009
Angular Distribution of Photoelectrons Cooper, J.; Zare, R. N. The Journal of Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1063/1.1668742	journal	January 1968
Channel switching in above-threshold ionization of xenon Schyja, V.; Lang, T.; Helm, H. Physical Review A, Vol. 57, Issue 5 https://doi.org/10.1103/PhysRevA.57.3692	journal	May 1998
Optical activity of the super-atom molecular orbital (SAMO) states in Li@C60+ conformers Mignolet, B.; Campbell, Eleanor E. B.; Remacle, F. PROCEEDINGS OF THE INTERNATIONAL CONFERENCE OF COMPUTATIONAL METHODS IN SCIENCES AND ENGINEERING 2017 (ICCMSE-2017), AIP Conference Proceedings https://doi.org/10.1063/1.5012307	conference	January 2017
Conductance and EPR study of the endohedral fullerene Li@C60 Popok, V. N.; Azarko, I. I.; Gromov, A. V. Solid State Communications, Vol. 133, Issue 8 https://doi.org/10.1016/j.ssc.2004.12.014	journal	February 2005
Spatially resolved conductance of oriented C ₆₀ Schull, G.; Néel, N.; Becker, M. New Journal of Physics, Vol. 10, Issue 6 https://doi.org/10.1088/1367-2630/10/6/065012	journal	June 2008
Thermal desorption spectroscopy of fullerene films containing endohedral Li@C 60 Kusch, C.; Krawez, N.; Tellgmann, R. Applied Physics A: Materials Science & Processing, Vol. 66, Issue 3 https://doi.org/10.1007/s003390050669	journal	March 1998
Fourier Transform Infrared and Raman Spectroscopic Study of Chromatographically Isolated Li@C ₆₀ and Li@C ₇₀ Gromov, Andrei; Ostrovskii, Denis; Lassesson, Andreas The Journal of Physical Chemistry B, Vol. 107, Issue 41 https://doi.org/10.1021/jp030403w	journal	October 2003
Electronic spectra and transitions of the fullerene C60 Leach, Sydney; Vervloet, Michel; Desprès, Alain Chemical Physics, Vol. 160, Issue 3 https://doi.org/10.1016/0301-0104(92)80012-K	journal	March 1992
Electron-spectroscopy study of ${LiC}_{60} :$ Charge transfer and dimer formation Schnadt, J.; Brühwiler, P. A.; Mårtensson, N. Physical Review B, Vol. 62, Issue 7 https://doi.org/10.1103/PhysRevB.62.4253	journal	August 2000
Third-Order Susceptibility of Li@C60 Campbell, Eleanor E. B.; Couris, Stelios; Fanti, Marianna Advanced Materials, Vol. 11, Issue 5 https://doi.org/10.1002/(SICI)1521-4095(199903)11:5<405::AID-ADMA405>3.0.CO;2-9	journal	March 1999
Erratum: Angular Distribution of Photoelectrons Cooper, J.; Zare, R. N. The Journal of Chemical Physics, Vol. 49, Issue 9 https://doi.org/10.1063/1.1670761	journal	November 1968
Visible and ultraviolet photoelectron spectroscopy of fullerenes using femtosecond laser pulses Johansson, J. O.; Henderson, G. G.; Campbell, E. E. B. EPJ Web of Conferences, Vol. 41 https://doi.org/10.1051/epjconf/20134102015	journal	January 2013
Endohedral fullerene production Tellgmann, R.; Krawez, N.; Lin, S. -H. Nature, Vol. 382, Issue 6590 https://doi.org/10.1038/382407a0	journal	August 1996
Preparation of endohedral fullerene containing lithium (Li@C60) and isolation as pure hexafluorophosphate salt ([Li+@C60][PF6−]) Okada, Hiroshi; Komuro, Takashi; Sakai, Takeshi RSC Advances, Vol. 2, Issue 28 https://doi.org/10.1039/c2ra21244g	journal	January 2012
Relative Photoionization Cross Sections of Super-Atom Molecular Orbitals (SAMOs) in C ₆₀ Bohl, Elvira; Sokół, Katarzyna P.; Mignolet, Benoit The Journal of Physical Chemistry A, Vol. 119, Issue 47 https://doi.org/10.1021/acs.jpca.5b10339	journal	November 2015
Tunneling Motion and Antiferroelectric Ordering of Lithium Cations Trapped inside Carbon Cages Aoyagi, Shinobu; Tokumitu, Akio; Sugimoto, Kunihisa Journal of the Physical Society of Japan, Vol. 85, Issue 9 https://doi.org/10.7566/JPSJ.85.094605	journal	September 2016
A layered ionic crystal of polar Li@C60 superatoms Aoyagi, Shinobu; Nishibori, Eiji; Sawa, Hiroshi Nature Chemistry, Vol. 2, Issue 8 https://doi.org/10.1038/nchem.698	journal	June 2010
Hot electron production and diffuse excited states in C ₇₀ , C ₈₂ , and Sc ₃ N@C ₈₀ characterized by angular-resolved photoelectron spectroscopy Olof Johansson, J.; Bohl, Elvira; Henderson, Gordon G. The Journal of Chemical Physics, Vol. 139, Issue 8 https://doi.org/10.1063/1.4818987	journal	August 2013
Atomlike, Hollow-Core-Bound Molecular Orbitals of C60 Feng, M.; Zhao, J.; Petek, H. Science, Vol. 320, Issue 5874 https://doi.org/10.1126/science.1155866	journal	April 2008
Probing Rapidly-Ionizing Super-Atom Molecular Orbitals in C ₆₀ : A Computational and Femtosecond Photoelectron Spectroscopy Study Mignolet, Benoît; Johansson, J. Olof; Campbell, Eleanor E. B. ChemPhysChem, Vol. 14, Issue 14 https://doi.org/10.1002/cphc.201300585	journal	August 2013
Lanthanum complexes of spheroidal carbon shells Heath, J. R.; O'Brien, S. C.; Zhang, Q. Journal of the American Chemical Society, Vol. 107, Issue 25 https://doi.org/10.1021/ja00311a102	journal	December 1985
Interactions between fullerene (C60) and endohedral alkali atoms Dunlap, B. I.; Ballester, J. L.; Schmidt, P. P. The Journal of Physical Chemistry, Vol. 96, Issue 24 https://doi.org/10.1021/j100203a038	journal	November 1992
Rotational dynamics of endohedral C60 fullerene complexes Hernández-Rojas, J.; Bretón, J.; Gomez Llorente, J. M. Journal of Physics and Chemistry of Solids, Vol. 58, Issue 11 https://doi.org/10.1016/S0022-3697(97)00053-X	journal	November 1997
Endohedral metallofullerenes Shinohara, H. Reports on Progress in Physics, Vol. 63, Issue 6 https://doi.org/10.1088/0034-4885/63/6/201	journal	May 2000
Super-atom molecular orbital excited states of fullerenes Johansson, J. Olof; Bohl, Elvira; Campbell, Eleanor E. B. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 374, Issue 2076 https://doi.org/10.1098/rsta.2015.0322	journal	September 2016
C60 as a Faraday cage Delaney, P.; Greer, J. C. Applied Physics Letters, Vol. 84, Issue 3 https://doi.org/10.1063/1.1640783	journal	January 2004
Dynamics of Thermal Electron Emission from Highly Excited C ₆₀ Johansson, J. Olof; Henderson, Gordon G.; Campbell, Eleanor E. B. The Journal of Physical Chemistry A, Vol. 118, Issue 37 https://doi.org/10.1021/jp408147f	journal	November 2013
Photoionisation and photofragmentation of Li@C60 Rohmund, F.; Bulgakov, A. V.; Hedén, M. Chemical Physics Letters, Vol. 323, Issue 1-2 https://doi.org/10.1016/S0009-2614(00)00443-7	journal	June 2000
Photoemission study of Li@C60 Yagi, Hajime; Ogasawara, Naoko; Zenki, Masashi Chemical Physics Letters, Vol. 651 https://doi.org/10.1016/j.cplett.2016.03.040	journal	May 2016
The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites Zhao, Jin; Feng, Min; Yang, Jinlong ACS Nano, Vol. 3, Issue 4 https://doi.org/10.1021/nn800834k	journal	March 2009
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) Yanai, Takeshi; Tew, David P.; Handy, Nicholas C. Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57 https://doi.org/10.1016/j.cplett.2004.06.011	journal	July 2004
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
Single-photon ionization of C60- and C70-fullerene with synchrotron radiation: determination of the ionization potential of C60 de Vries, J.; Steger, H.; Kamke, B. Chemical Physics Letters, Vol. 188, Issue 3-4 https://doi.org/10.1016/0009-2614(92)90001-4	journal	January 1992
Enhanced Photoinduced Electron-Transfer Reduction of Li ⁺ @C ₆₀ in Comparison with C ₆₀ Kawashima, Yuki; Ohkubo, Kei; Fukuzumi, Shunichi The Journal of Physical Chemistry A, Vol. 116, Issue 36 https://doi.org/10.1021/jp3059036	journal	August 2012
Imaging isodensity contours of molecular states with STM Reecht, Gaël; Heinrich, Benjamin W.; Bulou, Hervé New Journal of Physics, Vol. 19, Issue 11 https://doi.org/10.1088/1367-2630/aa969a	journal	November 2017
Current-Driven Dynamics in Molecular Junctions: Endohedral Fullerenes Jorn, Ryan; Zhao, Jin; Petek, Hrvoje ACS Nano, Vol. 5, Issue 10 https://doi.org/10.1021/nn202589p	journal	September 2011
Production and LDMS characterisation of endohedral alkalifullerene films Campbell, E. E. B.; Tellgmann, R.; Krawez, N. Journal of Physics and Chemistry of Solids, Vol. 58, Issue 11 https://doi.org/10.1016/S0022-3697(97)00063-2	journal	November 1997
Lix@C60: Calculations of the Encapsulation Energetics and Thermodynamics Slanina, Zdeněk; Uhlík, Filip; Lee, Shyi-Long International Journal of Molecular Sciences, Vol. 9, Issue 9 https://doi.org/10.3390/ijms9091841	journal	September 2008
Electronic structure of Li+@C60: Photoelectron spectroscopy of the Li+@C60[PF6−] salt and STM of the single Li+@C60 molecules on Cu(111) Yamada, Yoichi; Kuklin, Artem V.; Sato, Sho Carbon, Vol. 133 https://doi.org/10.1016/j.carbon.2018.02.106	journal	July 2018

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