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

doi:10.1021/acs.jpca.9b04966

Cited by 26 publications

(54 citation statements)

References 40 publications

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“…In that sense these molecules are similar to the previously studied "solvated electron precursors" (SEPs), where an SEP is a complex that consists of M(L) n q+ core (M = metal, L = ligand) with one or few diffuse electrons [45][46][47][48][49][50]. Interestingly, SEPs populate atomic p-, d-, f-, and g-type orbitals in excited states.…”

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confidence: 60%

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

Ariyarathna

2021

Int J of Quantum Chemistry

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The idea of designing unprecedented materials made of superatomic building blocks, motivated the present study on endohedral M@C 20 H 20 (M = Li, Na, Mg + ) species. Ground and excited electronic structures of M@C 20 H 20 (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 C 20 H 20 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@C 20 H 20 and Na@C 20 H 20 is 1s, 1p, 1d, 2s, 1f, 2p, 2d, 1g, 2f slightly different from that of Mg@C 20 H 20 + 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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confidence: 60%

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

Ariyarathna

2021

Int J of Quantum Chemistry

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“…The vibrational frequencies are helpful in identifying isomers and the arrangement of solvated ion clusters. In this sense, gas-phase infrared (IR) spectroscopy has been employed along with DFT calculations to derive structural information on solvated ions in the gas phase. ,,, To the best of our knowledge, experimental IR spectra have been reported only for the neutral and cationic Mg(NH 3 ) + and Ca(NH 3 ) n 0,+ species, , thus a direct comparison with our theoretical predictions was not possible. The calculated spectra are shown in Figures and .…”

Section: Resultsmentioning

confidence: 99%

Mg(II) and Ca(II) Microsolvation by Ammonia: Born–Oppenheimer Molecular Dynamics Studies

León-Pimentel

Saint-Martı́n²,

Ramı́rez-Solı́s

2021

J. Phys. Chem. A

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We report the structural and energetic features of the Mg2+ and Ca2+ cations in ammonia microsolvation environments. Born–Oppenhemier molecular dynamics studies are carried out for [Mg(NH3) n ]2+ and [Ca(NH3) n ]2+ clusters with n = 2, 3, 4, 6, 8, 20, and 27 at 300 K based on hybrid density functional theory calculations. We determine binding energies per ammonia molecule and the metal cation solvation patterns as a function of the number of molecules. The general trend for Mg2+ is that the Mg–N distances increase as a function of n until the first solvation shell is populated by six ammonia molecules, and then the distances slightly decrease while CN = 6 does not change. For Ca2+, the first solvation shell at room temperature is populated by eight ammonia molecules for clusters with more than one solvation shell, leading to a different structure from that of [Ca(NH3)6]2+ hexamine. The evaporation of NH3 molecules was found at 300 K only for Mg2+ clusters with n ≥ 10; this was not the case for Ca2+ clusters. Vibrational spectra are obtained for all of the clusters, and the evolution of the main features is discussed. EXAFS spectra are also presented for the [Mg(NH3)27(NH3)27]2+ and [Ca(NH3)27]2+ clusters, which yield valuable data to be compared with experimental data in the liquid phase, as previously done for the aqueous solvation of these dications.

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“…In that sense these molecules are similar to the previously studied"solvated electron precursors" (SEPs), where an SEP is a complex that consists of M(L) n q+ core (M = metal, L = ligand) with one or few diffuse electrons. [42][43][44][45][46][47] Interestingly, SEPs populate atomic p-, d-, f-, and g-type orbitals in excited states. The exact Aufbau order introduced for the M(NH 3 ) 4 (M = Li, Na) SEPs is 1s, 1p, 1d, 2s, 2p.…”

Section: Introductionmentioning

confidence: 99%

Superatomic Nature of Metal Encapsulated Dodecahedrane: The Case of M@C20H20 (M = Li, Na, Mg+)

Ariyarathna

2021

Preprint

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The idea of designing unprecedented materials made of superatomic building blocks, motivated the present study on endohedral M@C20H20 (M = Li, Na, Mg+) species. 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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Stability and Electronic Features of Calcium Hexa-, Hepta-, and Octa-Coordinated Ammonia Complexes: A First-Principles Study

Cited by 26 publications

References 40 publications

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

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

Mg(II) and Ca(II) Microsolvation by Ammonia: Born–Oppenheimer Molecular Dynamics Studies

Superatomic Nature of Metal Encapsulated Dodecahedrane: The Case of M@C20H20 (M = Li, Na, Mg+)

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Stability and Electronic Features of Calcium Hexa-, Hepta-, and Octa-Coordinated Ammonia Complexes: A First-Principles Study

Cited by 26 publications

References 40 publications

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

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

Mg(II) and Ca(II) Microsolvation by Ammonia: Born–Oppenheimer Molecular Dynamics Studies

Superatomic Nature of Metal Encapsulated Dodecahedrane: The Case of M@C20H20 (M = Li, Na, Mg+)

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Product

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

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