Superatom

In chemistry, a superatom is any cluster of atoms that seem to exhibit some of the properties of elemental atoms.^[1]

Sodium atoms, when cooled from vapor, naturally condense into clusters, preferentially containing a magic number of atoms (2, 8, 20, 40, 58, etc.), with the outermost electron of each atom entering an orbital encompassing all the atoms in the cluster. Superatoms tend to behave chemically in a way that will allow them to have a closed shell of electrons, in this new counting scheme.^{[citation needed]}

Aluminum clusters

Certain aluminum clusters have superatom properties. These aluminium clusters are generated as anions (Al⁻
_n with n = 1, 2, 3, … ) in helium gas and reacted with a gas containing iodine. When analyzed by mass spectrometry one main reaction product turns out to be Al
₁₃I⁻
.^[2] These clusters of 13 aluminium atoms with an extra electron added do not appear to react with oxygen when it is introduced in the same gas stream, indicating a halide-like character and a magic number of 40 free electrons. Such a cluster is known as a superhalogen.^[3]^[4]^[5]^[6] The cluster component in Al
₁₃I⁻
ion is similar to an iodide ion or better still a bromide ion. The related Al
₁₃I⁻
₂ cluster is expected to behave chemically like the triiodide ion.^[2]

Similarly it has been noted that Al
₁₄ clusters with 42 electrons (2 more than the magic numbers) appear to exhibit the properties of an alkaline earth metal which typically adopt +2 valence states. This is only known to occur when there are at least 3 iodine atoms attached to an Al⁻
₁₄ cluster, Al
₁₄I⁻
₃. The anionic cluster has a total of 43 itinerant electrons, but the three iodine atoms each remove one of the itinerant electrons to leave 40 electrons in the jellium shell.^[7]^[8]

It is particularly easy and reliable to study atomic clusters of inert gas atoms by computer simulation because interaction between two atoms can be approximated very well by the Lennard-Jones potential. Other methods are readily available and it has been established that the magic numbers are 13, 19, 23, 26, 29, 32, 34, 43, 46, 49, 55, etc.^[9]

Al
₇ = the property is similar to germanium atoms.
Al
₁₃ = the property is similar to halogen atoms, more specifically, chlorine.
- Al
  ₁₃I⁻
  _x, where x = 1–13.^[10]
Al
₁₄ = the property is similar to alkaline earth metals.
- Al
  ₁₄I⁻
  _x, where x = 1–14.^[10]
Al
₂₃
Al
₃₇
Al
₅O⁻
₄^[11]

Other clusters

Li(HF)₃Li = the (HF)₃ interior causes 2 valence electrons from the Li to orbit the entire molecule as if it were an atom's nucleus.^[12]
Li(NH₃)₄ = Has one diffuse electron orbiting around Li(NH₃)+4 core, i.e., mimics an alkali-metal atom.^[13]^[14]
Be(NH₃)₄ = Has two diffuse electrons orbiting around Be(NH₃)2+4 core, i.e., mimics He-atom.^[15]^[14]

VSi₁₆F = has ionic bonding.^[16]
A cluster of 13 platinum atoms becomes highly paramagnetic, much more so than platinum itself.^[17]
A cluster of 2,000 rubidium atoms.^[18]

Superatom complexes

Superatom complexes are a special group of superatoms that incorporate a metal core which is stabilized by organic ligands. In thiolate-protected gold cluster complexes a simple electron counting rule can be used to determine the total number of electrons ( $n e$ ) which correspond to a magic number via,

n_{e}=N\nu _{A}-M-z

where $N$ is the number of metal atoms (A) in the core, $v$ is the atomic valence, $M$ is the number of electron withdrawing ligands, and $z$ is the overall charge on the complex.^[19] For example the Au₁₀₂(p-MBA)₄₄ has 58 electrons and corresponds to a closed shell magic number.^[20]

Gold superatom complexes

Au₂₅(SMe)−18^[21]
Au₁₀₂(p⁻MBA)₄₄
Au₁₄₄(SR)₆₀^[22]

Other superatom complexes

Ga₂₃(N(Si(CH₃)₃)₂)₁₁^[23]
Al₅₀(C₅(CH₃)₅)₁₂^[24]
Re₆Se₈Cl₂ – In 2018 researchers produced 15-nm-thick flakes of this superatomic material. They anticipate that a monolayer will be a superatomic 2-D semiconductor and offer new 2-D materials with unusual, tunable properties.^[25]
Organo− Zintl-based superatoms:[Ge₉(CHO)₃] and [Ge₉(CHO)]^[26]

References

^ Ariyarathna, Isuru R. (21 December 2021). "Superatomic Chelates: The Cases of Metal Aza-Crown Ethers and Cryptands". Inorganic Chemistry. 61 (1): 579–585. doi:10.1021/acs.inorgchem.1c03261. PMID 34932345.
^ ^a ^b Bergeron, D. E. (2 April 2004). "Formation of Al
₁₃I⁻
: Evidence for the Superhalogen Character of Al13". Science. 304 (5667). American Association for the Advancement of Science (AAAS): 84–87. doi:10.1126/science.1093902. ISSN 0036-8075. PMID 15066775. S2CID 26728239.
^ Reddy, G. Naaresh; Parida, Rakesh; Giri, Santanab (2017-12-12). "Functionalized deltahedral Zintl complexes Ge9R3 (R = CF3, CN, and NO2): a new class of superhalogens". Chemical Communications. 53 (99): 13229–13232. doi:10.1039/C7CC08120K. ISSN 1364-548X. PMID 29182179.
^ Giri, Santanab; Child, Brandon Z.; Jena, Puru (2014). "Organic Superhalogens". ChemPhysChem. 15 (14): 2903–2908. doi:10.1002/cphc.201402472. ISSN 1439-7641. PMID 25056518.
^ Reddy, Gorre Naaresh; Giri, Santanab (2016-05-10). "Super/hyperhalogen aromatic heterocyclic compounds". RSC Advances. 6 (52): 47145–47150. Bibcode:2016RSCAd...647145R. doi:10.1039/C6RA08625J. ISSN 2046-2069.
^ Sinha, Swapan; Jena, Puru; Giri, Santanab (2022-08-12). "Functionalized nona-silicide [Si9R3] Zintl clusters: a new class of superhalogens". Physical Chemistry Chemical Physics. 24 (35): 21105–21111. Bibcode:2022PCCP...2421105S. doi:10.1039/D2CP02619H. ISSN 1463-9084. OSTI 1978872. PMID 36018293. S2CID 251551751.
^ Philip Ball, "A New Kind of Alchemy", New Scientist Issue dated 2005-04-16.
^ Bergeron, D. E. (14 January 2005). "Al Cluster Superatoms as Halogens in Polyhalides and as Alkaline Earths in Iodide Salts". Science. 307 (5707). American Association for the Advancement of Science (AAAS): 231–235. Bibcode:2005Sci...307..231B. doi:10.1126/science.1105820. ISSN 0036-8075. PMID 15653497. S2CID 8003390.
^ Harris, I. A.; Kidwell, R. S.; Northby, J. A. (17 December 1984). "Structure of Charged Argon Clusters Formed in a Free Jet Expansion". Physical Review Letters. 53 (25). American Physical Society (APS): 2390–2393. Bibcode:1984PhRvL..53.2390H. doi:10.1103/physrevlett.53.2390. ISSN 0031-9007. S2CID 13793440.
^ ^a ^b Naiche Owen Jones, 2006.^{[permanent dead link]}
^ Das, Ujjal; Raghavachari, Krishnan (2008). "Al5O4 Superatom with Potential for New Materials Design". Journal of Chemical Theory and Computation. 4 (12): 2011–2019. doi:10.1021/ct800232b. PMID 26620474.
^ Sun, Xiao-Ying; Li, Zhi-Ru; Wu, Di; Sun, Chia-Chung (2007). "Extraordinary superatom containing double shell nucleus: Li(HF)₃Li connected mainly by intermolecular interactions". International Journal of Quantum Chemistry. 107 (5). Wiley: 1215–1222. Bibcode:2007IJQC..107.1215S. doi:10.1002/qua.21246. ISSN 0020-7608.
^ Ariyarathna, Isuru R.; Pawłowski, Filip; Ortiz, Joseph Vincent; Miliordos, Evangelos (2018). "Molecules mimicking atoms: monomers and dimers of alkali metal solvated electron precursors". Physical Chemistry Chemical Physics. 20 (37): 24186–24191. Bibcode:2018PCCP...2024186A. doi:10.1039/C8CP05497E. ISSN 1463-9076. PMID 30209476.
^ ^a ^b Ariyarathna, Isuru (2021-03-01). First Principle Studies on Ground and Excited Electronic States: Chemical Bonding in Main-Group Molecules, Molecular Systems with Diffuse Electrons, and Water Activation using Transition Metal Monoxides (PhD thesis).
^ Ariyarathna, Isuru R.; Khan, Shahriar N.; Pawłowski, Filip; Ortiz, Joseph Vincent; Miliordos, Evangelos (2018-01-04). "Aufbau Rules for Solvated Electron Precursors: Be(NH 3 ) 4 2+ Complexes and Beyond". The Journal of Physical Chemistry Letters. 9 (1): 84–88. doi:10.1021/acs.jpclett.7b03000. ISSN 1948-7185. PMID 29232138.
^ Koyasu, Kiichirou; Atobe, Junko; Akutsu, Minoru; Mitsui, Masaaki; Nakajima, Atsushi (2007). "Electronic and Geometric Stabilities of Clusters with Transition Metal Encapsulated by Silicon". The Journal of Physical Chemistry A. 111 (1). American Chemical Society (ACS): 42–49. Bibcode:2007JPCA..111...42K. doi:10.1021/jp066757f. ISSN 1089-5639. PMID 17201386.
^ Platinum nanoclusters go magnetic Archived 2007-10-15 at the Wayback Machine, nanotechweb.org, 2007
^ Ultra Cold Trap Yields Superatom, NIST, 1995
^ Walter, M.; Akola, J.; Lopez-Acevedo, O.; Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Whetten, R. L.; Gronbeck, H.; Hakkinen, H. (1 June 2008). "A unified view of ligand-protected gold clusters as superatom complexes". Proceedings of the National Academy of Sciences. 105 (27): 9157–9162. Bibcode:2008PNAS..105.9157W. doi:10.1073/pnas.0801001105. ISSN 0027-8424. PMC 2442568. PMID 18599443.
^ Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.; Kornberg, R. D. (19 October 2007). "Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 Å Resolution". Science. 318 (5849). American Association for the Advancement of Science (AAAS): 430–433. Bibcode:2007Sci...318..430J. doi:10.1126/science.1148624. ISSN 0036-8075. PMID 17947577. S2CID 1566019.
^ Akola, Jaakko; Walter, Michael; Whetten, Robert L.; Häkkinen, Hannu; Grönbeck, Henrik (2008). "On the Structure of Thiolate-Protected Au₂₅". Journal of the American Chemical Society. 130 (12). American Chemical Society (ACS): 3756–3757. doi:10.1021/ja800594p. ISSN 0002-7863. PMID 18321117.
^ Lopez-Acevedo, Olga; Akola, Jaakko; Whetten, Robert L.; Grönbeck, Henrik; Häkkinen, Hannu (16 January 2009). "Structure and Bonding in the Ubiquitous Icosahedral Metallic Gold Cluster Au₁₄₄(SR)₆₀". The Journal of Physical Chemistry C. 113 (13). American Chemical Society (ACS): 5035–5038. doi:10.1021/jp8115098. ISSN 1932-7447.
^ Hartig, Jens; Stößer, Anna; Hauser, Petra; Schnöckel, Hansgeorg (26 February 2007). "A Metalloid Ga₂₃{N(SiMe₃)₂}₁₁ Cluster: The Jellium Model Put to Test". Angewandte Chemie International Edition. 46 (10). Wiley: 1658–1662. doi:10.1002/anie.200604311. ISSN 1433-7851. PMID 17230594.
^ Clayborne, Peneé A.; Lopez-Acevedo, Olga; Whetten, Robert L.; Grönbeck, Henrik; Häkkinen, Hannu (13 May 2011). "The Al₅₀Cp*₁₂ Cluster – A 138-Electron Closed Shell (L = 6) Superatom". European Journal of Inorganic Chemistry. 2011 (17). Wiley: 2649–2652. doi:10.1002/ejic.201100374. ISSN 1434-1948.
^ Zyga, Lisa. "Researchers create first superatomic 2-D semiconductor". Phys.org. Retrieved 2018-02-18.
^ Reddy, G. Naaresh; Jena, Puru; Giri, Santanab (2017-10-16). "Organo−Zintl-based superatoms: [Ge9(CHO)3] and [Ge9(CHO)]". Chemical Physics Letters. 686: 195–202. Bibcode:2017CPL...686..195R. doi:10.1016/j.cplett.2017.08.056. ISSN 0009-2614.

External links

Designer Magnetic Superatoms, J.U. Reveles, et al. 2009
Gold Superatom Complexes, M. Walter et al. 2008
Gold Superatom Complexes P.D. Jadzinsky et al. 2007
Multiple Valence Superatoms, J.U. Reveles, S.N. Khanna, P.J. Roach, and A.W. Castleman Jr., 2006
On the Aluminum Cluster Superatoms acting as Halogens and Alkaline-earth Metals, Bergeron, Dennis E et al., 2006
Clusters of Aluminum Atoms Found to Have Properties of Other Elements Reveal a New Form of Chemistry, innovations report, 2005. Have a picture of Al₁₄.
Clusters of Aluminum Atoms Found to Have Properties of Other Elements Reveal a New Form of Chemistry, Penn State, Eberly College of Science, 2005
Research Reveals Halogen Characteristics innovations report, 2004. Have pictures of Al₁₃.

[1] Ariyarathna, Isuru R. (21 December 2021). "Superatomic Chelates: The Cases of Metal Aza-Crown Ethers and Cryptands". Inorganic Chemistry. 61 (1): 579–585. doi:10.1021/acs.inorgchem.1c03261. PMID 34932345.

[bergeron/2004-2] Bergeron, D. E. (2 April 2004). "Formation of Al
₁₃I⁻
: Evidence for the Superhalogen Character of Al13". Science. 304 (5667). American Association for the Advancement of Science (AAAS): 84–87. doi:10.1126/science.1093902. ISSN 0036-8075. PMID 15066775. S2CID 26728239.

[3] Reddy, G. Naaresh; Parida, Rakesh; Giri, Santanab (2017-12-12). "Functionalized deltahedral Zintl complexes Ge9R3 (R = CF3, CN, and NO2): a new class of superhalogens". Chemical Communications. 53 (99): 13229–13232. doi:10.1039/C7CC08120K. ISSN 1364-548X. PMID 29182179.

[4] Giri, Santanab; Child, Brandon Z.; Jena, Puru (2014). "Organic Superhalogens". ChemPhysChem. 15 (14): 2903–2908. doi:10.1002/cphc.201402472. ISSN 1439-7641. PMID 25056518.

[5] Reddy, Gorre Naaresh; Giri, Santanab (2016-05-10). "Super/hyperhalogen aromatic heterocyclic compounds". RSC Advances. 6 (52): 47145–47150. Bibcode:2016RSCAd...647145R. doi:10.1039/C6RA08625J. ISSN 2046-2069.

[6] Sinha, Swapan; Jena, Puru; Giri, Santanab (2022-08-12). "Functionalized nona-silicide [Si9R3] Zintl clusters: a new class of superhalogens". Physical Chemistry Chemical Physics. 24 (35): 21105–21111. Bibcode:2022PCCP...2421105S. doi:10.1039/D2CP02619H. ISSN 1463-9084. OSTI 1978872. PMID 36018293. S2CID 251551751.

[ball-7] Philip Ball, "A New Kind of Alchemy", New Scientist Issue dated 2005-04-16.

[bergeron/2005-8] Bergeron, D. E. (14 January 2005). "Al Cluster Superatoms as Halogens in Polyhalides and as Alkaline Earths in Iodide Salts". Science. 307 (5707). American Association for the Advancement of Science (AAAS): 231–235. Bibcode:2005Sci...307..231B. doi:10.1126/science.1105820. ISSN 0036-8075. PMID 15653497. S2CID 8003390.

[9] Harris, I. A.; Kidwell, R. S.; Northby, J. A. (17 December 1984). "Structure of Charged Argon Clusters Formed in a Free Jet Expansion". Physical Review Letters. 53 (25). American Physical Society (APS): 2390–2393. Bibcode:1984PhRvL..53.2390H. doi:10.1103/physrevlett.53.2390. ISSN 0031-9007. S2CID 13793440.

[N.O.Jones-10] Naiche Owen Jones, 2006.^{[permanent dead link]}

[11] Das, Ujjal; Raghavachari, Krishnan (2008). "Al5O4 Superatom with Potential for New Materials Design". Journal of Chemical Theory and Computation. 4 (12): 2011–2019. doi:10.1021/ct800232b. PMID 26620474.

[12] Sun, Xiao-Ying; Li, Zhi-Ru; Wu, Di; Sun, Chia-Chung (2007). "Extraordinary superatom containing double shell nucleus: Li(HF)₃Li connected mainly by intermolecular interactions". International Journal of Quantum Chemistry. 107 (5). Wiley: 1215–1222. Bibcode:2007IJQC..107.1215S. doi:10.1002/qua.21246. ISSN 0020-7608.

[13] Ariyarathna, Isuru R.; Pawłowski, Filip; Ortiz, Joseph Vincent; Miliordos, Evangelos (2018). "Molecules mimicking atoms: monomers and dimers of alkali metal solvated electron precursors". Physical Chemistry Chemical Physics. 20 (37): 24186–24191. Bibcode:2018PCCP...2024186A. doi:10.1039/C8CP05497E. ISSN 1463-9076. PMID 30209476.

[thesis-14] Ariyarathna, Isuru (2021-03-01). First Principle Studies on Ground and Excited Electronic States: Chemical Bonding in Main-Group Molecules, Molecular Systems with Diffuse Electrons, and Water Activation using Transition Metal Monoxides (PhD thesis).

[15] Ariyarathna, Isuru R.; Khan, Shahriar N.; Pawłowski, Filip; Ortiz, Joseph Vincent; Miliordos, Evangelos (2018-01-04). "Aufbau Rules for Solvated Electron Precursors: Be(NH 3 ) 4 2+ Complexes and Beyond". The Journal of Physical Chemistry Letters. 9 (1): 84–88. doi:10.1021/acs.jpclett.7b03000. ISSN 1948-7185. PMID 29232138.

[16] Koyasu, Kiichirou; Atobe, Junko; Akutsu, Minoru; Mitsui, Masaaki; Nakajima, Atsushi (2007). "Electronic and Geometric Stabilities of Clusters with Transition Metal Encapsulated by Silicon". The Journal of Physical Chemistry A. 111 (1). American Chemical Society (ACS): 42–49. Bibcode:2007JPCA..111...42K. doi:10.1021/jp066757f. ISSN 1089-5639. PMID 17201386.

[17] Platinum nanoclusters go magnetic Archived 2007-10-15 at the Wayback Machine, nanotechweb.org, 2007

[18] Ultra Cold Trap Yields Superatom, NIST, 1995

[19] Walter, M.; Akola, J.; Lopez-Acevedo, O.; Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Whetten, R. L.; Gronbeck, H.; Hakkinen, H. (1 June 2008). "A unified view of ligand-protected gold clusters as superatom complexes". Proceedings of the National Academy of Sciences. 105 (27): 9157–9162. Bibcode:2008PNAS..105.9157W. doi:10.1073/pnas.0801001105. ISSN 0027-8424. PMC 2442568. PMID 18599443.

[20] Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.; Kornberg, R. D. (19 October 2007). "Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 Å Resolution". Science. 318 (5849). American Association for the Advancement of Science (AAAS): 430–433. Bibcode:2007Sci...318..430J. doi:10.1126/science.1148624. ISSN 0036-8075. PMID 17947577. S2CID 1566019.

[21] Akola, Jaakko; Walter, Michael; Whetten, Robert L.; Häkkinen, Hannu; Grönbeck, Henrik (2008). "On the Structure of Thiolate-Protected Au₂₅". Journal of the American Chemical Society. 130 (12). American Chemical Society (ACS): 3756–3757. doi:10.1021/ja800594p. ISSN 0002-7863. PMID 18321117.

[22] Lopez-Acevedo, Olga; Akola, Jaakko; Whetten, Robert L.; Grönbeck, Henrik; Häkkinen, Hannu (16 January 2009). "Structure and Bonding in the Ubiquitous Icosahedral Metallic Gold Cluster Au₁₄₄(SR)₆₀". The Journal of Physical Chemistry C. 113 (13). American Chemical Society (ACS): 5035–5038. doi:10.1021/jp8115098. ISSN 1932-7447.

[23] Hartig, Jens; Stößer, Anna; Hauser, Petra; Schnöckel, Hansgeorg (26 February 2007). "A Metalloid Ga₂₃{N(SiMe₃)₂}₁₁ Cluster: The Jellium Model Put to Test". Angewandte Chemie International Edition. 46 (10). Wiley: 1658–1662. doi:10.1002/anie.200604311. ISSN 1433-7851. PMID 17230594.

[24] Clayborne, Peneé A.; Lopez-Acevedo, Olga; Whetten, Robert L.; Grönbeck, Henrik; Häkkinen, Hannu (13 May 2011). "The Al₅₀Cp*₁₂ Cluster – A 138-Electron Closed Shell (L = 6) Superatom". European Journal of Inorganic Chemistry. 2011 (17). Wiley: 2649–2652. doi:10.1002/ejic.201100374. ISSN 1434-1948.

[25] Zyga, Lisa. "Researchers create first superatomic 2-D semiconductor". Phys.org. Retrieved 2018-02-18.

[26] Reddy, G. Naaresh; Jena, Puru; Giri, Santanab (2017-10-16). "Organo−Zintl-based superatoms: [Ge9(CHO)3] and [Ge9(CHO)]". Chemical Physics Letters. 686: 195–202. Bibcode:2017CPL...686..195R. doi:10.1016/j.cplett.2017.08.056. ISSN 0009-2614.

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Superatom

Aluminum clusters

Other clusters

Superatom complexes

Gold superatom complexes

Other superatom complexes

See also

References

External links

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