Actinyl cation–cation interactions in the gas phase: an accurate thermochemical study

Feng, Rulin; Glendening, Eric D.; Peterson, Kirk A.

doi:10.1039/c9cp00760a

Actinyl cation–cation interactions in the gas phase: an accurate thermochemical study

Journal Article · Fri Mar 22 00:00:00 EDT 2019 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c9cp00760a· OSTI ID:1611063

Feng, Rulin ^[1]; Glendening, Eric D. ^[2]; ^[3]

Washington State Univ., Pullman, WA (United States); Washington State University
Indiana State Univ., Terre Haute, IN (United States)
Washington State Univ., Pullman, WA (United States)

Gas phase actinyl cation–cation interactions (CCIs) were studied by an accurate composite coupled cluster thermochemical approach for the first time. A number of CCI dimers were constructed from the monomers UO₂²⁺, UO₂⁺, NpO₂²⁺, NpO₂⁺, PuO₂⁺, and AmO₂⁺. All CCI dimers studied were calculated to be thermodynamically unstable, with dissociation energies ranging from -60 to -90 kcal mol^-1, but in many cases kinetic stability was indicated by calculated local minima with well depths as large as ~15 kcal mol-1. Most of the dimers studied involved a T-shaped geometry, although one side-on dimer, (UO2+)₂, was included since it was amenable to coupled cluster methods. In the T-shaped isomers the most stable dimers were calculated to arise when the oxo-group of an An(V) actinyl cation was oriented towards the metal center of an An(VI) actinyl cation. For both mixed-valent An(VI)/An(V) and mono-valent An(V) dimers, the stability as estimated from the depth of the calculated local minimum decreased in the donor series U(V) > Np(V) > Pu(V) > Am(V). These trends correlate well with experimental trends in condensed phase CCIs. A rationale for the bonding in CCIs was investigated by carrying out charge transfer analyses using the natural bond orbital (NBO) method. Augmenting the usual Lewis acid-base explanation, CCIs are the direct result of a competition between charge transfer stabilization, which can be as much as 0.11e or 30.7 kcal mol^-1 at equilibrium, and Coulombic repulsive destabilization.

View Accepted Manuscript (DOE)

Research Organization:: Washington State Univ., Pullman, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008501

OSTI ID:: 1611063

Alternate ID(s):: OSTI ID: 1503922

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 15 Vol. 21; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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