Ab initio calculations of heavy-actinide hexahalide compounds: Do these heavy actinides behave like their isoelectronic lanthanide analogues?

Cristian Celis-Barros, Dayán Páez-Hernández, María J. Beltrán-Leiva, Ramiro Arratia-Perez

Resultado de la investigación: Article

  • 1 Citas

Resumen

Research on heavy actinides has experienced an increased interest in the last few years due to new synthetic techniques and recent technological advances that have allowed for obtaining important information even from very small samples. This area presents challenges not only from the experimental point of view but also from the theoretical perspective. This work deals with a multiconfigurational CASSCF and NEVPT2 benchmark study based on a two-step methodology that considers first correlation effects and then the spin-orbit coupling applied to berkelium (Bk), californium (Cf), einsteinium (Es) and fermium (Fm) hexahalides. Optical properties, such as f → d transitions and crystal-field parameters, have been calculated and rationalized. The results for these trivalent actinides indicate that the electronic structure of the low-lying states is reproduced accurately with small basis sets. The ground-state multiplets are isolated, in the same manner as their isoelectronic lanthanide counterparts. In the case of tetravalent berkelium, the picture is different regarding the electronic structure where crystal-field theory fails due to considerable ligand-to-metal charge transfer contributions to the ground state.

IdiomaEnglish
Páginas4038-4049
Número de páginas12
PublicaciónPhysical Chemistry Chemical Physics
Volumen20
Número de edición6
DOI
EstadoPublished - 1 ene 2018

Huella dactilar

Berkelium
berkelium
Actinoid Series Elements
Lanthanoid Series Elements
Fermium
Einsteinium
Ground state
crystal field theory
Electronic structure
einsteinium
Californium
fermium
californium
analogs
electronic structure
Crystals
ground state
Charge transfer
Orbits
Optical properties

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Citar esto

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title = "Ab initio calculations of heavy-actinide hexahalide compounds: Do these heavy actinides behave like their isoelectronic lanthanide analogues?",
abstract = "Research on heavy actinides has experienced an increased interest in the last few years due to new synthetic techniques and recent technological advances that have allowed for obtaining important information even from very small samples. This area presents challenges not only from the experimental point of view but also from the theoretical perspective. This work deals with a multiconfigurational CASSCF and NEVPT2 benchmark study based on a two-step methodology that considers first correlation effects and then the spin-orbit coupling applied to berkelium (Bk), californium (Cf), einsteinium (Es) and fermium (Fm) hexahalides. Optical properties, such as f → d transitions and crystal-field parameters, have been calculated and rationalized. The results for these trivalent actinides indicate that the electronic structure of the low-lying states is reproduced accurately with small basis sets. The ground-state multiplets are isolated, in the same manner as their isoelectronic lanthanide counterparts. In the case of tetravalent berkelium, the picture is different regarding the electronic structure where crystal-field theory fails due to considerable ligand-to-metal charge transfer contributions to the ground state.",
author = "Cristian Celis-Barros and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Beltr{\'a}n-Leiva, {Mar{\'i}a J.} and Ramiro Arratia-Perez",
year = "2018",
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doi = "10.1039/c7cp06585j",
language = "English",
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T1 - Ab initio calculations of heavy-actinide hexahalide compounds

T2 - Physical Chemistry Chemical Physics

AU - Celis-Barros, Cristian

AU - Páez-Hernández, Dayán

AU - Beltrán-Leiva, María J.

AU - Arratia-Perez, Ramiro

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Research on heavy actinides has experienced an increased interest in the last few years due to new synthetic techniques and recent technological advances that have allowed for obtaining important information even from very small samples. This area presents challenges not only from the experimental point of view but also from the theoretical perspective. This work deals with a multiconfigurational CASSCF and NEVPT2 benchmark study based on a two-step methodology that considers first correlation effects and then the spin-orbit coupling applied to berkelium (Bk), californium (Cf), einsteinium (Es) and fermium (Fm) hexahalides. Optical properties, such as f → d transitions and crystal-field parameters, have been calculated and rationalized. The results for these trivalent actinides indicate that the electronic structure of the low-lying states is reproduced accurately with small basis sets. The ground-state multiplets are isolated, in the same manner as their isoelectronic lanthanide counterparts. In the case of tetravalent berkelium, the picture is different regarding the electronic structure where crystal-field theory fails due to considerable ligand-to-metal charge transfer contributions to the ground state.

AB - Research on heavy actinides has experienced an increased interest in the last few years due to new synthetic techniques and recent technological advances that have allowed for obtaining important information even from very small samples. This area presents challenges not only from the experimental point of view but also from the theoretical perspective. This work deals with a multiconfigurational CASSCF and NEVPT2 benchmark study based on a two-step methodology that considers first correlation effects and then the spin-orbit coupling applied to berkelium (Bk), californium (Cf), einsteinium (Es) and fermium (Fm) hexahalides. Optical properties, such as f → d transitions and crystal-field parameters, have been calculated and rationalized. The results for these trivalent actinides indicate that the electronic structure of the low-lying states is reproduced accurately with small basis sets. The ground-state multiplets are isolated, in the same manner as their isoelectronic lanthanide counterparts. In the case of tetravalent berkelium, the picture is different regarding the electronic structure where crystal-field theory fails due to considerable ligand-to-metal charge transfer contributions to the ground state.

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