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Related: About this forumSingle Molecule Magnets Exploiting the 5f Electrons of Plutonium.
The paper I'll discuss in this brief post is this one: Theoretical Investigation of Plutonium-Based Single-Molecule Magnets (Carlo Alberto Gaggioli and Laura Gagliardi,* Inorg. Chem., 2018, 57 (14), pp 80988105).
From a purely theoretical standpoint, plutonium is one of the most interesting elements in the periodic table. It's huge array of electrons and orbitals, traveling around a heavy nucleus and thus requiring the electrons to travel at relativistic speeds, a significant fraction of the speed of light, the shielding these electrons bring, the fact that it has a nearly half filled set of f orbitals and its myriad oxidation states and habit of disproportionation (oxidizing and reducing itself simultaneously), never mind its radiation effects all combine to produce a real sense of fascination.
A surprising paper, published this year, (the paper cited above) suggest that plutonium species are worthy of study because of a potential (but perhaps not practical) use in computer hardware. (Perhaps it can at least elucidate a path to other elements, in particular lanthanides, perhaps cerium.)
Or perhaps not, from the introductory text:
...The actinide elements instead, because of their large spinorbit coupling and the radial extension of the 5f orbitals, are more promising for the design of both mononuclear and exchange coupled molecules. Indeed, new actinide SMMs have emerged and are already demonstrating encouraging properties.(18−25) The actinides present a non-negligible covalency of the metalligand interaction,(26,27) and while covalency offers an advantage for the generation of strong magnetic exchange, it also makes the rational design of mononuclear actinide complexes more challenging than in the lanthanide case.
However, after some very sophisticated computer modeling the authors note that such a mononuclear complex of plutonium has been synthesized. It is here:
The caption:
It is known to be exhibit magnetic susceptibility, which the authors explore from a theoretical standpoint with a sophisticated computational analytical method:
The electronic structures were further characterized using multireference methods. The wave functions were optimized at the complete active space self-consistent field (CASSCF)(38) level of theory. All-electron basis sets of atomic natural orbital type with relativistic core corrections (ANO-RCC) were used,(63) employing a triple-ζ plus polarization basis set for Pu (VTZP) and double-ζ plus polarization basis set for the other atoms (VDZP). The resolution of identity Cholesky decomposition (RICD)(64) was employed to reduce the time for the computation of the two-electron integrals. Scalar relativistic effects were included by means of the DouglasKrollHess Hamiltonian.(65)
The smallest active space employed in this work is a CASSCF(5,7) active space, meaning five electrons and seven orbitals, which takes into account all the configuration state functions (CSFs) arising from the distributions of the five electrons of Pu(III) in the seven 5f orbitals. This active space gives rise to 21 sextet, 224 quartet, and 490 doublet roots. We further examined an enlarged active space [CASSCF(5,12)], in which we included the five unoccupied 6d orbitals of plutonium, to account for possible low-energy 5f to 6d excitations...
...We then performed a multistate CASPT2 calculation (MS-CASPT2)(66) using an IPEA shift of 0.25 and an imaginary shift of 0.2 atomic unit on a selected set of states (vide infra). Spinorbit (SO) coupling effects were estimated a posteriori by using the RAS state interaction (SO-RASSI) method.(67)
Finally, we computed the magnetic susceptibilities with the SINGLE-ANISO code,(68−70) which requests as input energies (ε ) and magnetic moments (μ ) of the spinorbit states obtained from the RASSI calculation and uses them in an equation based on the van-Vleck formalism (eq 1).
The magnetic susceptibility is a function of temperature and arises from the sum over the spin states (i,j) of the magnetic moments weighted by the Boltzmann population of each state. The magnetic moments are calculated by applying the magnetic moment operator in the basis of multiplet eigenstates.(71) The magnetic moment operator reads
where ge (=2.0023) is the free spin g factor, μB is the Bohr magneton, and Ŝ and L̂ are the operators of the total spin momentum and the total orbital momentum, respectively.
The summations run over all electrons of the complex.
For compound 1, the calculations described above were also performed at the experimental geometry to confirm that the two different geometries give similar results.
It might be lots of jargon, but it gives a feel for the task...
The authors determine the energies of various electronic states, which is described in the following graphic:
The caption:
And the point of the calculation, the magnetic susceptibility:
The caption:
The success of a model really depends on how closely it matches experiment.
The authors comment:
But in their conclusion the authors note that they are on the path to success:
It will be interesting to see if someone is able to synthesize the improved complex they predict will be superior.
It is difficult to imagine that plutonium based computer hardware will ever be practical of course; the reason for doing this work, besides testing theory that might be useful in other areas with other elements, is that it is extends pure knowledge, it causes to stretch our scientific intellectual muscles to inspire wonder.
Of, course, in the abstract, one notes that plutonium has at least two isotopes with very long half-lives, and thus lower radioactivity, that one might imagine might be sufficiently stable to build such a device, Pu-242 and Pu-244. The latter isotope has a half-life of 80 million years. However Pu-244 is very difficult to access. Other than atom-by-atom synthesis in an accelerator, the generation of this isotope is extremely complex, particularly if one is seeking high isotopic purity. It would involve the long term irradiation of pure americium, with the goal of displacing as much as the lower readily available isotope, Am-241, with the higher isotope, Am-243. This would require periods of irradiation punctuated by separations to remove resultant Pu-238 (from the decay of Cm-242) and Pu-242 (also from the branched decay of Cm-242), until reasonably pure Am-243 resulted for a final irradiation. Pu-244 arises from one branch (the minor branch, about 1%) of the decay of Am-244. The separation would need to take place fairly early, since the other isotope produced from the decay of Am-244, Cm-244, decays with an 18 year half life to a contaminating isotope (and neutron emitter) Pu-240.
...Not worth it I think.
Nevertheless, the paper itself was worth a read, because it's fun, and interesting, and it expands one's mind.
I hope your New Year's plans are proceeding nicely. Have fun and be safe.
TexasTowelie
(112,087 posts)The professor that I had never deviated from the textbook so the only thing I had to do was bring a highlighter to class.
I understood about 80% of that discussion.
Victor_c3
(3,557 posts).... and the other articles that youve provided.
As the guy above mentioned, I only get about 80% of it, but I appreciate the mental workout and a the bit of understanding that I did gain.
Since my retirement nearly four years ago, Ive missed working in the field of chemistry. Im only 38 so I guess its possible that I could go back to work, but Im doubtful. In the meantime, I certainly enjoy the articles you post.