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Ground and excited states analysis of alkali metal ethylenediamine and crown ether complexes.
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In this paper, high-level electronic structure calculations are carried out to obtain optimized geometries and excitation energies of neutral lithium, sodium, and potassium complexes with two ethylenediamine and one or two crown ether molecules.Abstract:
High-level electronic structure calculations are carried out to obtain optimized geometries and excitation energies of neutral lithium, sodium, and potassium complexes with two ethylenediamine and one or two crown ether molecules. Three different sizes of crowns are employed (12-crown-4, 15-crown-5, 18-crown-6). The ground state of all complexes contains an electron in an s-type orbital. For the mono-crown ether complexes, this orbital is the polarized valence s-orbital of the metal, but for the other systems this orbital is a peripheral diffuse orbital. The nature of the low-lying electronic states is found to be different for each of these species. Specifically, the metal ethylenediamine complexes follow the previously discovered shell model of metal ammonia complexes (1s, 1p, 1d, 2s, 1f), but both mono- and sandwich di-crown ether complexes bear a different shell model partially due to their lower (cylindrical) symmetry and the stabilization of the 2s-type orbital. Li(15-crown-5) is the only complex with the metal in the middle of the crown ether and adopts closely the shell model of metal ammonia complexes. Our findings suggest that the electronic band structure of electrides (metal crown ether sandwich aggregates) and expanded metals (metal ammonia aggregates) should be different despite the similar nature of these systems (bearing diffuse electrons around a metal complex).read more
Citations
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Can boron form coordination complexes with diffuse electrons? Evidence for linked solvated electron precursors
TL;DR: In this paper , density functional theory and ab initio multi-reference calculations are performed to examine the stability and electronic structure of boron complexes that host diffuse electrons in their periphery, and the results indicate that the excitation energies are nearly independent of the chain length for four carbon atoms or longer.
Journal ArticleDOI
Introducing Novel Materials with Diffuse Electrons for Applications in Redox Catalysis and Quantum Computing via Theoretical Calculations
TL;DR: In this article , gas phase calculations are performed on isolated (NH3)3LiNH2(CH2)1-10H2NLi(NH 3)3 molecular strings.
Journal ArticleDOI
Ab Initio Calculations on the Ground and Excited Electronic States of Thorium–Ammonia, Thorium–Aza-Crown, and Thorium–Crown Ether Complexes
TL;DR: The ground and excited states of an f-block metal-ammonia complex with ammonia, crown ethers, and aza-crown ethers were investigated in this article .
References
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Walter Kohn,L. J. Sham +1 more
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Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
TL;DR: In this paper, a detailed study of correlation effects in the oxygen atom was conducted, and it was shown that primitive basis sets of primitive Gaussian functions effectively and efficiently describe correlation effects.
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Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functions
TL;DR: In this paper, a reliable procedure for calculating the electron affinity of an atom and present results for hydrogen, boron, carbon, oxygen, and fluorine (hydrogen is included for completeness).
Journal ArticleDOI
Note on an Approximation Treatment for Many-Electron Systems
Chr. Møller,Milton S. Plesset +1 more
TL;DR: In this article, a perturbation theory for treating a system of n electrons in which the Hartree-Fock solution appears as the zero-order approximation was developed, and it was shown by this development that the first order correction for the energy and the charge density of the system is zero.