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Thermochemistry of Elementary Actinide Sulfide Molecules: A Gas-Phase Study of Curium Sulfide

Published online by Cambridge University Press:  01 February 2011

Cláudia C. L. Pereira ,
Joaquim Marçalo  and
John K. Gibson
Cláudia C. L. Pereira
Affiliation:
[email protected], Instituto Tecnológico e Nuclear, Unidade de Ciências Químicas e Radiofarmacêuticas, Sacavém, Portugal
Joaquim Marçalo
Affiliation:
[email protected], Instituto Tecnológico e Nuclear, Unidade de Ciências Químicas e Radiofarmacêuticas, Sacavém, Portugal
John K. Gibson
Affiliation:
[email protected], Lawrence Berkeley National Laboratory, Chemical Sciences Division, Berkeley, California, United States
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Abstract

Experiments to explore the reactivity and thermochemistry of elementary transuranium sulfide molecules have been initiated to expand the basis for a fundamental understanding of actinide bonding, and to enable the development of advanced theoretical methodologies which will be of general applicability to more complex molecular systems. Bimolecular gas-phase reactions between transuranium actinide ions and neutral reagents are employed to obtain thermochemical information. The initial actinide sulfide studies have focused on obtaining the 298 K bond dissociation energy for the CmS+ ion, D[Cm+-S] = 475±37 kJ mol-1; from this result and an estimate of IE[CmS] ≈ IE[CmO] + 0.5 eV, we obtain D[Cm-S] = 563±64 kJ mol-1. The bond dissociation energies, D[Cm+-S] and D[Cm-S] are approximately 200 kJ mol-1 and 150 kJ mol-1 lower than for the corresponding oxides, CmO+ and CmO. The nature of the bonding in the CmS+ ion appears to be generally similar to that in other oxophilic metal sulfides. Comparisons with previous bond dissociation energies reported for ThS and US may suggest a difference in the An-S bonds for these early actinide sulfides as compared with CmS.

Keywords

actinidemass spectroscopyS
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1264: Symposia Z/BB – Basic Actinide Science and Materials for Nuclear Applications , 2010 , 1264-Z02-04
Copyright
Copyright © Materials Research Society 2010

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