Observation of electron orbital signatures of single atoms within metal-phthalocyanines using atomic force microscopy

Chen, Pengcheng; Fan, Dingxin; Selloni, Annabella; Carter, Emily A.; Arnold, Craig B.; Zhang, Yunlong; Gross, Adam S.; Chelikowsky, James R.; Yao, Nan

doi:10.1038/s41467-023-37023-9

Title: Observation of electron orbital signatures of single atoms within metal-phthalocyanines using atomic force microscopy

Journal Article · Thu Mar 16 00:00:00 EDT 2023 · Nature Communications

DOI:https://doi.org/10.1038/s41467-023-37023-9· OSTI ID:1996982

Chen, Pengcheng ^[1]; Fan, Dingxin ^[2];

^[1];

^[3];

^[4];

^[5];

^[6];

^[1]

Princeton University, NJ (United States)
Princeton University, NJ (United States); University of Texas, Austin, TX (United States)
Princeton University, NJ (United States); Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)
Princeton University, NJ (United States);
ExxonMobil Technology and Engineering Company, Annandale, NJ (United States)
University of Texas, Austin, TX (United States)

Resolving the electronic structure of a single atom within a molecule is of fundamental importance for understanding and predicting chemical and physical properties of functional molecules such as molecular catalysts. However, the observation of the orbital signature of an individual atom is challenging. We report here the direct identification of two adjacent transition-metal atoms, Fe and Co, within phthalocyanine molecules using high-resolution noncontact atomic force microscopy (HR-AFM). HR-AFM imaging reveals that the Co atom is brighter and presents four distinct lobes on the horizontal plane whereas the Fe atom displays a “square” morphology. Pico-force spectroscopy measurements show a larger repulsion force of about 5 pN on the tip exerted by Co in comparison to Fe. Our combined experimental and theoretical results demonstrate that both the distinguishable features in AFM images and the variation in the measured forces arise from Co’s higher electron orbital occupation above the molecular plane. The ability to directly observe orbital signatures using HR-AFM should provide a promising approach to characterizing the electronic structure of an individual atom in a molecular species and to understand mechanisms of certain chemical reactions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)

Sponsoring Organization:: USDOE; National Science Foundation (NSF); Welch Foundation

Grant/Contract Number:: AC02-09CH11466; DMR-2011750; F-2094

OSTI ID:: 1996982

Journal Information:: Nature Communications, Vol. 14, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (37)

Surface chemistry of porphyrins and phthalocyanines Gottfried, J. Michael Surface Science Reports, Vol. 70, Issue 3 https://doi.org/10.1016/j.surfrep.2015.04.001	journal	November 2015
Identification of adsorbed molecules via STM tip manipulation: CO, H ₂ O, and O ₂ on TiO ₂ anatase (101) Setvin, Martin; Daniel, Benjamin; Aschauer, Ulrich Phys. Chem. Chem. Phys., Vol. 16, Issue 39 https://doi.org/10.1039/C4CP03212H	journal	January 2014
Chemical Identification of Single Atoms in Heterogeneous III–IV Chains on Si(100) Surface by Means of nc-AFM and DFT Calculations Setvín, Martin; Mutombo, Pingo; Ondráček, Martin ACS Nano, Vol. 6, Issue 8 https://doi.org/10.1021/nn301996k	journal	July 2012
The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy Gross, L.; Mohn, F.; Moll, N. Science, Vol. 325, Issue 5944 https://doi.org/10.1126/science.1176210	journal	August 2009
Orbital-Resolved Imaging of the Adsorbed State of Pyridine on GaP(110) Identifies Sites Susceptible to Nucleophilic Attack Kronawitter, Coleman X.; Lessio, Martina; Zahl, Percy The Journal of Physical Chemistry C, Vol. 119, Issue 52 https://doi.org/10.1021/acs.jpcc.5b08659	journal	December 2015
Remark on “algorithm 778: L-BFGS-B: Fortran subroutines for large-scale bound constrained optimization” Morales, José Luis; Nocedal, Jorge ACM Transactions on Mathematical Software, Vol. 38, Issue 1 https://doi.org/10.1145/2049662.2049669	journal	November 2011
Discovering rare-earth-free magnetic materials through the development of a database Sakurai, Masahiro; Wang, Renhai; Liao, Timothy Physical Review Materials, Vol. 4, Issue 11 https://doi.org/10.1103/PhysRevMaterials.4.114408	journal	November 2020
Accurate formulas for interaction force and energy in frequency modulation force spectroscopy Sader, John E.; Jarvis, Suzanne P. Applied Physics Letters, Vol. 84, Issue 10 https://doi.org/10.1063/1.1667267	journal	March 2004
Imaging the wave functions of adsorbed molecules Luftner, D.; Ules, T.; Reinisch, E. M. Proceedings of the National Academy of Sciences, Vol. 111, Issue 2 https://doi.org/10.1073/pnas.1315716110	journal	December 2013
Atomic Fingerprinting of Heteroatoms Using Noncontact Atomic Force Microscopy Fan, Dingxin; Chelikowsky, James R. Small, Vol. 17, Issue 51 https://doi.org/10.1002/smll.202102977	journal	October 2021
H2Pc and pentacene on Cu(110)-(2×1)O: A combined STM and nc-AFM study Garlant, Angel; Maughan, Bret; Zahl, Percy Surface Science, Vol. 696 https://doi.org/10.1016/j.susc.2020.121590	journal	June 2020
Electronic and magnetic properties of molecule-metal interfaces: Transition-metal phthalocyanines adsorbed on Ag(100) Mugarza, A.; Robles, R.; Krull, C. Physical Review B, Vol. 85, Issue 15 https://doi.org/10.1103/PhysRevB.85.155437	journal	April 2012
Chemical identification of individual surface atoms by atomic force microscopy Sugimoto, Yoshiaki; Pou, Pablo; Abe, Masayuki Nature, Vol. 446, Issue 7131 https://doi.org/10.1038/nature05530	journal	March 2007
Hydrogen Atoms under Magnification: Direct Observation of the Nodal Structure of Stark States Stodolna, A. S.; Rouzée, A.; Lépine, F. Physical Review Letters, Vol. 110, Issue 21 https://doi.org/10.1103/PhysRevLett.110.213001	journal	May 2013
Nanostructured transition-metal phthalocyanine complexes for catalytic oxygen reduction reaction Chen, Siyu; Xu, Zhanwei; Li, Jiayin Nanotechnology, Vol. 33, Issue 18 https://doi.org/10.1088/1361-6528/ac4cef	journal	February 2022
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
Finite-difference-pseudopotential method: Electronic structure calculations without a basis Chelikowsky, James R.; Troullier, N.; Saad, Y. Physical Review Letters, Vol. 72, Issue 8 https://doi.org/10.1103/PhysRevLett.72.1240	journal	February 1994
Visualization of the Molecular Jahn-Teller Effect in an Insulating K4C60 Monolayer Wachowiak, A. Science, Vol. 310, Issue 5747 https://doi.org/10.1126/science.1117303	journal	October 2005
Combined orbital tomography study of multi-configurational molecular adsorbate systems Kliuiev, Pavel; Zamborlini, Giovanni; Jugovac, Matteo Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13254-7	journal	November 2019
PARSEC – the pseudopotential algorithm for real-space electronic structure calculations: recent advances and novel applications to nano-structures Kronik, Leeor; Makmal, Adi; Tiago, Murilo L. physica status solidi (b), Vol. 243, Issue 5 https://doi.org/10.1002/pssb.200541463	journal	April 2006
Breaking a dative bond with mechanical forces Chen, Pengcheng; Fan, Dingxin; Zhang, Yunlong Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25932-6	journal	September 2021
Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor Nguyen, Giang D.; Tsai, Hsin-Zon; Omrani, Arash A. Nature Nanotechnology, Vol. 12, Issue 11 https://doi.org/10.1038/nnano.2017.155	journal	September 2017
Real-space imaging of molecular structure and chemical bonding by single-molecule inelastic tunneling probe Chiang, C. -l.; Xu, C.; Han, Z. Science, Vol. 344, Issue 6186 https://doi.org/10.1126/science.1253405	journal	May 2014
Discrimination of Bond Order in Organic Molecules Using Noncontact Atomic Force Microscopy Fan, Dingxin; Sakai, Yuki; Chelikowsky, James R. Nano Letters, Vol. 19, Issue 8 https://doi.org/10.1021/acs.nanolett.9b02097	journal	July 2019
Subatomic resolution force microscopy reveals internal structure and adsorption sites of small iron clusters Emmrich, M.; Huber, F.; Pielmeier, F. Science, Vol. 348, Issue 6232 https://doi.org/10.1126/science.aaa5329	journal	March 2015
Guide for Atomic Force Microscopy Image Analysis To Discriminate Heteroatoms in Aromatic Molecules Zahl, Percy; Zhang, Yunlong Energy & Fuels, Vol. 33, Issue 6 https://doi.org/10.1021/acs.energyfuels.9b00165	journal	April 2019
Reaction Mechanisms of Well-Defined Metal-N ₄ Sites in Electrocatalytic CO ₂ Reduction Zhang, Zheng; Xiao, Jianping; Chen, Xue-Jiao Angewandte Chemie International Edition, Vol. 57, Issue 50 https://doi.org/10.1002/anie.201808593	journal	November 2018
Chemical bond formation showing a transition from physisorption to chemisorption Huber, Ferdinand; Berwanger, Julian; Polesya, Svitlana Science, Vol. 366, Issue 6462 https://doi.org/10.1126/science.aay3444	journal	September 2019
Chemical and steric effects in simulating noncontact atomic force microscopy images of organic molecules on a Cu (111) substrate Fan, Dingxin; Sakai, Yuki; Chelikowsky, James R. Physical Review Materials, Vol. 4, Issue 5 https://doi.org/10.1103/PhysRevMaterials.4.053802	journal	May 2020
Electronegativity determination of individual surface atoms by atomic force microscopy Onoda, Jo; Ondráček, Martin; Jelínek, Pavel Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15155	journal	April 2017
Scalable implementation of polynomial filtering for density functional theory calculation in PARSEC Liou, Kai-Hsin; Yang, Chao; Chelikowsky, James R. Computer Physics Communications, Vol. 254 https://doi.org/10.1016/j.cpc.2020.107330	journal	September 2020
Real-Space Identification of Intermolecular Bonding with Atomic Force Microscopy Zhang, J.; Chen, P.; Yuan, B. Science, Vol. 342, Issue 6158 https://doi.org/10.1126/science.1242603	journal	September 2013
High harmonic interferometry of multi-electron dynamics in molecules Smirnova, Olga; Mairesse, Yann; Patchkovskii, Serguei Nature, Vol. 460, Issue 7258 https://doi.org/10.1038/nature08253	journal	July 2009
Bond-Order Discrimination by Atomic Force Microscopy Gross, L.; Mohn, F.; Moll, N. Science, Vol. 337, Issue 6100 https://doi.org/10.1126/science.1225621	journal	September 2012
Direct quantitative measurement of the C═O⋅⋅⋅H–C bond by atomic force microscopy Kawai, Shigeki; Nishiuchi, Tomohiko; Kodama, Takuya Science Advances, Vol. 3, Issue 5 https://doi.org/10.1126/sciadv.1603258	journal	May 2017
High-Resolution Molecular Orbital Imaging Using a $p$ -Wave STM Tip Gross, Leo; Moll, Nikolaj; Mohn, Fabian Physical Review Letters, Vol. 107, Issue 8 https://doi.org/10.1103/PhysRevLett.107.086101	journal	August 2011
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965

Similar Records

Chemical and steric effects in simulating noncontact atomic force microscopy images of organic molecules on a Cu (111) substrate

Journal Article · Wed May 27 00:00:00 EDT 2020 · Physical Review Materials · OSTI ID:1996982

Fan, Dingxin; Sakai, Yuki; Chelikowsky, James R.

Identifying site-dependent effects of an extra Co atom on electronic states of single Co-phthalocyanine molecule

Journal Article · Tue Jul 21 00:00:00 EDT 2015 · Journal of Chemical Physics · OSTI ID:1996982

Li, Jingcheng; Wang, Yu; Li, Bin; +2 more

Atomic Fingerprinting of Heteroatoms Using Noncontact Atomic Force Microscopy

Journal Article · Fri Oct 01 00:00:00 EDT 2021 · Small · OSTI ID:1996982

Fan, Dingxin; Chelikowsky, James R.

Related Subjects

36 MATERIALS SCIENCE
Electronic properties and materials
Scanning probe microscopy
Two-dimensional materials

Title: Observation of electron orbital signatures of single atoms within metal-phthalocyanines using atomic force microscopy

Citation Formats

References (37)

Similar Records

Related Subjects