### Abstract

The ground-state molecular properties of the trichlorides of light actinides (An = Th-Cm) have been predicted by state-of-the-art quantum chemical calculations. The ground electronic states have been determined by multireference calculations at the CASPT2 level including both scalar and spin-orbit relativistic effects. These studies supported the expected single-configuration character of ThCl_{3} and CmCl_{3} with their well-defined 6dσ/7s hybrid and 5f^{7} configurations, respectively. In contrast, the intermediate actinides (PaCl_{3}- AmCl_{3}) with partly filled 5f shells have numerous very low-lying excited states and consequently a mixed character of the spin-orbit ground states. Apart from the planar ThCl_{3} the ground-state molecular geometries proved to be pyramidal with C_{3v} symmetry. The gradually decreasing An-Cl bond distances reveal the actinide contraction known for the atomic and ionic radii of these actinide atoms. Other ground-state molecular properties as vibrational frequencies and natural charges have been obtained by density functional theory calculations using the B3LYP exchange-correlation functional in conjunction with small-core relativistic energy-consistent pseudopotentials for the actinides.

Original language | English |
---|---|

Pages (from-to) | 11357-11363 |

Number of pages | 7 |

Journal | Journal of Physical Chemistry A |

Volume | 117 |

Issue number | 44 |

DOIs | |

Publication status | Published - Nov 7 2013 |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

_{3}(An = Th-Cm).

*Journal of Physical Chemistry A*,

*117*(44), 11357-11363. https://doi.org/10.1021/jp407855j

**Structure and other molecular properties of actinide trichlorides AnCl _{3} (An = Th-Cm).** / Kovács, Attila; Konings, Rudy J M; Varga, Z.; Szieberth, D.

Research output: Contribution to journal › Article

_{3}(An = Th-Cm)',

*Journal of Physical Chemistry A*, vol. 117, no. 44, pp. 11357-11363. https://doi.org/10.1021/jp407855j

_{3}(An = Th-Cm). Journal of Physical Chemistry A. 2013 Nov 7;117(44):11357-11363. https://doi.org/10.1021/jp407855j

}

TY - JOUR

T1 - Structure and other molecular properties of actinide trichlorides AnCl 3 (An = Th-Cm)

AU - Kovács, Attila

AU - Konings, Rudy J M

AU - Varga, Z.

AU - Szieberth, D.

PY - 2013/11/7

Y1 - 2013/11/7

N2 - The ground-state molecular properties of the trichlorides of light actinides (An = Th-Cm) have been predicted by state-of-the-art quantum chemical calculations. The ground electronic states have been determined by multireference calculations at the CASPT2 level including both scalar and spin-orbit relativistic effects. These studies supported the expected single-configuration character of ThCl3 and CmCl3 with their well-defined 6dσ/7s hybrid and 5f7 configurations, respectively. In contrast, the intermediate actinides (PaCl3- AmCl3) with partly filled 5f shells have numerous very low-lying excited states and consequently a mixed character of the spin-orbit ground states. Apart from the planar ThCl3 the ground-state molecular geometries proved to be pyramidal with C3v symmetry. The gradually decreasing An-Cl bond distances reveal the actinide contraction known for the atomic and ionic radii of these actinide atoms. Other ground-state molecular properties as vibrational frequencies and natural charges have been obtained by density functional theory calculations using the B3LYP exchange-correlation functional in conjunction with small-core relativistic energy-consistent pseudopotentials for the actinides.

AB - The ground-state molecular properties of the trichlorides of light actinides (An = Th-Cm) have been predicted by state-of-the-art quantum chemical calculations. The ground electronic states have been determined by multireference calculations at the CASPT2 level including both scalar and spin-orbit relativistic effects. These studies supported the expected single-configuration character of ThCl3 and CmCl3 with their well-defined 6dσ/7s hybrid and 5f7 configurations, respectively. In contrast, the intermediate actinides (PaCl3- AmCl3) with partly filled 5f shells have numerous very low-lying excited states and consequently a mixed character of the spin-orbit ground states. Apart from the planar ThCl3 the ground-state molecular geometries proved to be pyramidal with C3v symmetry. The gradually decreasing An-Cl bond distances reveal the actinide contraction known for the atomic and ionic radii of these actinide atoms. Other ground-state molecular properties as vibrational frequencies and natural charges have been obtained by density functional theory calculations using the B3LYP exchange-correlation functional in conjunction with small-core relativistic energy-consistent pseudopotentials for the actinides.

UR - http://www.scopus.com/inward/record.url?scp=84887633177&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84887633177&partnerID=8YFLogxK

U2 - 10.1021/jp407855j

DO - 10.1021/jp407855j

M3 - Article

C2 - 24093335

AN - SCOPUS:84887633177

VL - 117

SP - 11357

EP - 11363

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 44

ER -