Superatomic nature of metal encapsulated dodecahedrane: The case of M@C20H20 (M = Li, Na, Mg+)

Ariyarathna, Isuru R.

doi:10.1002/qua.26774

Title: Superatomic nature of metal encapsulated dodecahedrane: The case of M@C₂₀H₂₀ (M = Li, Na, Mg⁺)

Journal Article · Sat Jul 17 00:00:00 EDT 2021 · International Journal of Quantum Chemistry

DOI:https://doi.org/10.1002/qua.26774· OSTI ID:1981433

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Auburn Univ., AL (United States)

The idea of designing unprecedented materials made of superatomic building blocks, motivated the present study on endohedral M@C₂₀H₂₀ (M = Li, Na, Mg⁺) species. Here, ground and excited electronic structures of M@C₂₀H₂₀ (M = Li, Na, Mg⁺) were analyzed by means of high-level quantum calculations. In their ground states, one electron occupies a defuse superatomic s-orbital that lies around the C₂₀H₂₀ cage. These entities populate higher angular momentum p-, d-, f-, g-superatomic orbitals in their low-lying electronic states. The proposed superatomic Aufbau shell model for Li@C₂₀H₂₀ and Na@C₂₀H₂₀ is 1s, 1p, 1d, 2s, 1f, 2p, 2d, 1g, 2f slightly different from that of Mg@C₂₀H₂₀⁺ which is 1s, 1p, 1d, 2s, 1f, 2p, 2d, 1g, 3s, 2f, 2g, 3p. These introduced superatomic orbital series resemble the Aufbau principle of solvated electron precursors.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1981433

Journal Information:: International Journal of Quantum Chemistry, Vol. 121, Issue 20; ISSN 0020-7608

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Probing the interior of fullerenes by 3He NMR spectroscopy of endohedral 3He@C60 and 3He@C70 Saunders, Martin; Jiménez-Vázquez, Hugo A.; Cross, R. James Nature, Vol. 367, Issue 6460 https://doi.org/10.1038/367256a0	journal	January 1994
Computed Relative Populations of D ₂ (22)-C ₈₄ Endohedrals with Encapsulated Monomeric and Dimeric Water Slanina, Zdeněk; Uhlík, Filip; Nagase, Shigeru ChemPhysChem, Vol. 17, Issue 8 https://doi.org/10.1002/cphc.201600076	journal	February 2016
DVM Xα calculations on the electronic structure of “superalkali” cations Gutsev, G. L.; Boldyrev, A. I. Chemical Physics Letters, Vol. 92, Issue 3 https://doi.org/10.1016/0009-2614(82)80272-8	journal	October 1982
An efficient, renormalized self-energy for calculating the electron binding energies of closed-shell molecules and anions Ortiz, J. V. International Journal of Quantum Chemistry, Vol. 105, Issue 6 https://doi.org/10.1002/qua.20664	journal	January 2005
Water clusters in a confined nonpolar environment Ramachandran, C. N.; Sathyamurthy, N. Chemical Physics Letters, Vol. 410, Issue 4-6 https://doi.org/10.1016/j.cplett.2005.04.113	journal	July 2005
Charge separated states of endohedral fullerene Li@C ₂₀ Yang, Yi-Fan; Gromov, Evgeniy V.; Cederbaum, Lorenz S. The Journal of Chemical Physics, Vol. 151, Issue 11 https://doi.org/10.1063/1.5120017	journal	September 2019
Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods Dolgounitcheva, O.; Díaz-Tinoco, Manuel; Zakrzewski, V. G. Journal of Chemical Theory and Computation, Vol. 12, Issue 2 https://doi.org/10.1021/acs.jctc.5b00872	journal	January 2016
Theoretical studies of dodecahedrane. 3. Ab initio studies of dodecahedrane and its inclusion compounds Disch, Raymond L.; Schulman, Jerome M. Journal of the American Chemical Society, Vol. 103, Issue 12 https://doi.org/10.1021/ja00402a012	journal	June 1981
Blue Shift in X−H Stretching Frequency of Molecules Due to Confinement Shameema, O.; Ramachandran, C. N.; Sathyamurthy, N. The Journal of Physical Chemistry A, Vol. 110, Issue 1 https://doi.org/10.1021/jp056027s	journal	December 2005
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
Aufbau Principle for Diffuse Electrons of Double-Shell Metal Ammonia Complexes: The Case of M(NH ₃ ) ₄ @12NH ₃ , M = Li, Be ⁺ , B ²⁺ Ariyarathna, Isuru R.; Pawłowski, Filip; Ortiz, Joseph Vincent The Journal of Physical Chemistry A, Vol. 124, Issue 3 https://doi.org/10.1021/acs.jpca.9b07734	journal	October 2019
Some new diatomic molecule containing endohedral fullerenes Peres, Tikva; Cao, Baopeng; Cui, Weidong International Journal of Mass Spectrometry, Vol. 210-211 https://doi.org/10.1016/S1387-3806(01)00420-1	journal	September 2001
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
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
Stable Compounds of Helium and Neon: He@C60 and Ne@C60 Saunders, M.; Jimenez-Vazquez, H. A.; Cross, R. J. Science, Vol. 259, Issue 5100 https://doi.org/10.1126/science.259.5100.1428	journal	March 1993
Calculations of the water-dimer encapsulations into C ₈₄ Slanina, Zdeněk; Uhlík, Filip; Lu, Xing Fullerenes, Nanotubes and Carbon Nanostructures, Vol. 24, Issue 1 https://doi.org/10.1080/1536383X.2015.1072515	journal	August 2015
Propagators in Quantum Chemistry Linderberg, Jan; Öhrn, Yngve https://doi.org/10.1002/0471721549	book	March 2004
The rise of inorganic nanomaterial implementation in food applications Ariyarathna, Isuru R.; Rajakaruna, R. M. P. I.; Karunaratne, D. Nedra Food Control, Vol. 77 https://doi.org/10.1016/j.foodcont.2017.02.016	journal	July 2017
Nano-encapsulation as a promising approach for targeted delivery and controlled release of vitamins Katouzian, Iman; Jafari, Seid Mahdi Trends in Food Science & Technology, Vol. 53 https://doi.org/10.1016/j.tifs.2016.05.002	journal	July 2016
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
Endohedral chemistry: electronic structures of molecules trapped inside the C60 cage Cioslowski, Jerzy Journal of the American Chemical Society, Vol. 113, Issue 11 https://doi.org/10.1021/ja00011a013	journal	May 1991
Fabrication and application of complex microcapsules: a review Bah, Mohamed Gibril; Bilal, Hafiz Muhammad; Wang, Jingtao Soft Matter, Vol. 16, Issue 3 https://doi.org/10.1039/C9SM01634A	journal	January 2020
Water-Dimer Stability and Its Fullerene Encapsulations Uhlík, Filip; Slanina, Zdeněk; Lee, Shyi-Long Journal of Computational and Theoretical Nanoscience, Vol. 12, Issue 6 https://doi.org/10.1166/jctn.2015.3835	journal	April 2015
Buckminsterfullerene C60: a chemical Faraday cage for atomic nitrogen Pietzak, B.; Waiblinger, M.; Murphy, T. Almeida Chemical Physics Letters, Vol. 279, Issue 5-6 https://doi.org/10.1016/S0009-2614(97)01100-7	journal	November 1997
Caged-electron states and split-electron states in the endohedral alkali C₆₀ Yang, Yi-Fan; Cederbaum, Lorenz S. Physical Chemistry Chemical Physics, Vol. 23, Issue 20 https://doi.org/10.1039/D1CP01341F	journal	January 2021
Caged-Electron States in Endohedral Li Fullerenes Yang, Yi-Fan; Gromov, Evgeniy V.; Cederbaum, Lorenz S. The Journal of Physical Chemistry Letters, Vol. 10, Issue 24 https://doi.org/10.1021/acs.jpclett.9b02934	journal	November 2019
Separation of N2@C60 and N@C60 Suetsuna, Tomohiro; Dragoe, Nita; Harneit, Wolfgang Chemistry - A European Journal, Vol. 8, Issue 22 https://doi.org/10.1002/1521-3765(20021115)8:22<5079::AID-CHEM5079>3.0.CO;2-H	journal	November 2002
Investigation into the molecular structure, electronic properties, and energetic stability of endohedral (TM@C 20 ) and exohedral (TM-C 20 ) metallofullerene derivatives of C 20 : TM = Group 11 and 12 transition metal atoms/ions Gonzalez, Mariela; Lujan, Samantha; Beran, Kyle A. Computational and Theoretical Chemistry, Vol. 1119 https://doi.org/10.1016/j.comptc.2017.09.013	journal	November 2017
Gaussian basis sets for use in correlated molecular calculations. VII. Valence, core-valence, and scalar relativistic basis sets for Li, Be, Na, and Mg Prascher, Brian P.; Woon, David E.; Peterson, Kirk A. Theoretical Chemistry Accounts, Vol. 128, Issue 1 https://doi.org/10.1007/s00214-010-0764-0	journal	May 2010
Interaction and dynamics of endohedral gas molecules in fullerene C60 isomers and C70 Williams, C. I.; Whitehead, M. A.; Pang, L. The Journal of Physical Chemistry, Vol. 97, Issue 45 https://doi.org/10.1021/j100147a017	journal	November 1993
Nanotechnological Strategies to Improve Water Solubility of Commercially Available Drugs Karunaratne, Desiree Nedra; Ariyarathna, Isuru R.; Welideniya, Dhanushi Current Nanomedicine, Vol. 7, Issue 2 https://doi.org/10.2174/2468187307666161227171349	journal	July 2017
H ₂ , Ne, and N ₂ Energies of Encapsulation into C ₆₀ Evaluated with the MPWB1K Functional Slanina, Zdeněk; Pulay, Peter; Nagase, Shigeru Journal of Chemical Theory and Computation, Vol. 2, Issue 3 https://doi.org/10.1021/ct0503320	journal	May 2006
A systematic review on nanoencapsulation of food bioactive ingredients and nutraceuticals by various nanocarriers Assadpour, Elham; Mahdi Jafari, Seid Critical Reviews in Food Science and Nutrition, Vol. 59, Issue 19 https://doi.org/10.1080/10408398.2018.1484687	journal	December 2018
Mechanical and electronic properties of endofullerene Ne@C₆₀studied via structure distortions Wang, Z. Y.; Su, K. H.; Fan, H. Q. Molecular Physics, Vol. 106, Issue 5 https://doi.org/10.1080/00268970801941791	journal	March 2008
Structures and Stabilities of Endo- and Exohedral Dodecahedrane Complexes (X@C₂₀H₂₀ and XC₂₀H₂₀, X = H⁺, H, N, P, C^-, Si^-, O⁺, S⁺) Chen, Zhongfang; Jiao, Haijun; Moran, Damian The Journal of Physical Chemistry A, Vol. 107, Issue 12 https://doi.org/10.1021/jp0273631	journal	March 2003
Aufbau Rules for Solvated Electron Precursors: Be(NH ₃ ) ₄ ^0,± Complexes and Beyond Ariyarathna, Isuru R.; Khan, Shahriar N.; Pawłowski, Filip The Journal of Physical Chemistry Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acs.jpclett.7b03000	journal	December 2017
Synthesis, Properties, and Applications of Hollow Micro-/Nanostructures Wang, Xiaojing; Feng, Ji; Bai, Yaocai Chemical Reviews, Vol. 116, Issue 18 https://doi.org/10.1021/acs.chemrev.5b00731	journal	May 2016
Observation of Atomlike Nitrogen in Nitrogen-Implanted Solid $C_{60}$ Almeida Murphy, T.; Pawlik, Th.; Weidinger, A. Physical Review Letters, Vol. 77, Issue 6 https://doi.org/10.1103/PhysRevLett.77.1075	journal	August 1996
Rotational motion of a single water molecule in a buckyball Farimani, A. Barati; Wu, Yanbin; Aluru, N. R. Physical Chemistry Chemical Physics, Vol. 15, Issue 41 https://doi.org/10.1039/c3cp53277a	journal	January 2013
Molecules mimicking atoms: monomers and dimers of alkali metal solvated electron precursors Ariyarathna, Isuru R.; Pawłowski, Filip; Ortiz, Joseph Vincent Physical Chemistry Chemical Physics, Vol. 20, Issue 37 https://doi.org/10.1039/C8CP05497E	journal	January 2018
Computational Comparison of the Water-Dimer Encapsulations intoD₂(22)-C₈₄andD_2d(23)-C₈₄ Slanina, Zdeněk; Uhlík, Filip; Nagase, Shigeru ECS Journal of Solid State Science and Technology, Vol. 6, Issue 6 https://doi.org/10.1149/2.0201706jss	journal	January 2017
Putting Helium Inside Dodecahedrane Cross, R. James; Saunders, Martin; Prinzbach, Horst Organic Letters, Vol. 1, Issue 9 https://doi.org/10.1021/ol991037v	journal	September 1999
Geometric and electronic structure analysis of calcium water complexes with one and two solvation shells Ariyarathna, Isuru R.; Miliordos, Evangelos Physical Chemistry Chemical Physics, Vol. 22, Issue 39 https://doi.org/10.1039/D0CP04309E	journal	January 2020
Fourier transform EPR study of N@C60 in solution Knapp, C.; Dinse, K. -P.; Pietzak, B. Chemical Physics Letters, Vol. 272, Issue 5-6 https://doi.org/10.1016/S0009-2614(97)00577-0	journal	July 1997
Is fullerene C₆₀ large enough to host an aromatic molecule? Mazurek, Aleksander P.; Sadlej-Sosnowska, Nina International Journal of Quantum Chemistry, Vol. 111, Issue 10 https://doi.org/10.1002/qua.22551	journal	April 2011
A computational characterization of N₂@C₆₀ Slanina, Zdenĕk; Nagase, Shigeru Molecular Physics, Vol. 104, Issue 20-21 https://doi.org/10.1080/00268970601041131	journal	October 2006
Can a Single Molecule of Water be Completely Isolated Within the Subnano-Space Inside the Fullerene C ₆₀ Cage? A Quantum Chemical Prospective Varadwaj, Arpita; Varadwaj, Pradeep R. Chemistry - A European Journal, Vol. 18, Issue 48 https://doi.org/10.1002/chem.201200969	journal	October 2012
Computing fullerene encapsulation of non-metallic molecules: N₂@C₆₀and NH₃@C₆₀ Slanina, Z.; Uhlík, F.; Adamowicz, L. Molecular Simulation, Vol. 31, Issue 12 https://doi.org/10.1080/08927020500283966	journal	October 2005
First-Principles Study of Electronic Transport Properties of Dodecahedrane C₂₀H₂₀ and Its Endohedral Complex Li@C₂₀H₂₀ An, Yi-Peng; Yang, Chuan-Lu; Wang, Mei-Shan The Journal of Physical Chemistry C, Vol. 113, Issue 35 https://doi.org/10.1021/jp904202c	journal	August 2009
Equation of motion coupled cluster method for electron attachment Nooijen, Marcel; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 102, Issue 9 https://doi.org/10.1063/1.468592	journal	March 1995
Movement of Ng 2 molecules confined in a C 60 cage: An ab initio molecular dynamics study Khatua, Munmun; Pan, Sudip; Chattaraj, Pratim K. Chemical Physics Letters, Vol. 610-611 https://doi.org/10.1016/j.cplett.2014.06.052	journal	August 2014
Structures, Stabilities, and Ionization Potentials of Dodecahedrane Endohedral Complexes Moran, Damian; Stahl, Frank; Jemmis, Eluvathingal D. The Journal of Physical Chemistry A, Vol. 106, Issue 20 https://doi.org/10.1021/jp014471z	journal	April 2002
Note on an Approximation Treatment for Many-Electron Systems Møller, Chr.; Plesset, M. S. Physical Review, Vol. 46, Issue 7 https://doi.org/10.1103/PhysRev.46.618	journal	October 1934
A comparison of the photochemical reactivity of N@C60 and C60: photolysis with disiliraneElectronic supplementary information (ESI) available: experimental results. See http://www.rsc.org/suppdata/cc/b3/b309470g/ Wakahara, Takatsugu; Matsunaga, Yoichiro; Katayama, Akira Chemical Communications, Issue 23 https://doi.org/10.1039/b309470g	journal	January 2003
A computational characterization of CO@C₆₀ Slanina, Zdeněk; Uhlík, Filip; Nagase, Shigeru Fullerenes, Nanotubes and Carbon Nanostructures, Vol. 25, Issue 11 https://doi.org/10.1080/1536383X.2017.1357548	journal	November 2017
The electronic structure of dodecahedrane and the nature of the central cavity Dixon, David A.; Deerfield, David; Graham, Glenn D. Chemical Physics Letters, Vol. 78, Issue 1 https://doi.org/10.1016/0009-2614(81)85576-5	journal	February 1981
Stability and Electronic Features of Calcium Hexa-, Hepta-, and Octa-Coordinated Ammonia Complexes: A First-Principles Study Ariyarathna, Isuru R.; Almeida, Nuno M. S.; Miliordos, Evangelos The Journal of Physical Chemistry A, Vol. 123, Issue 31 https://doi.org/10.1021/acs.jpca.9b04966	journal	July 2019
Molden: a pre- and post-processing program for molecular and electronic structures* Schaftenaar, G.; Noordik, J. H. Journal of Computer-Aided Molecular Design, Vol. 14, Issue 2, p. 123-134 https://doi.org/10.1023/A:1008193805436	journal	February 2000
Electron propagator theory: an approach to prediction and interpretation in quantum chemistry: Electron propagator theory Ortiz, Joseph Vincent Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 3, Issue 2 https://doi.org/10.1002/wcms.1116	journal	September 2012

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Title: Superatomic nature of metal encapsulated dodecahedrane: The case of M@C20H20 (M = Li, Na, Mg+)

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Title: Superatomic nature of metal encapsulated dodecahedrane: The case of M@C₂₀H₂₀ (M = Li, Na, Mg⁺)