Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties

Harindu Rajapaksha; Grant C. Benthin; Dmytro V. Kravchuk; Haley Lightfoot; Sara E. Mason; Tori Z. Forbes

doi:10.1021/acs.inorgchem.3c02502

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Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties

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Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties

Harindu Rajapaksha, Grant C. Benthin, Dmytro V. Kravchuk, Haley Lightfoot, Sara E. Mason and Tori Z. Forbes

Inorganic chemistry, Vol.62(42), pp.17265-17275

10/10/2023

DOI: 10.1021/acs.inorgchem.3c02502

PMCID: PMC10598792

PMID: 37816161

Appears in UI Libraries Support Open Access

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Abstract

Noncovalent interactions (NCIs) can influence the stability and chemical properties of pentavalent and hexavalent actinyl (AnO2+/2+) compounds. In this work, the impact of NCIs (actinyl–hydrogen and actinyl–cation interactions) on the enthalpy of formation (ΔHf) and vibrational features was evaluated using Np(VI) tetrachloro compounds as the model system. We calculated the ΔHf values of these solid-state compounds through density functional theory+ thermodynamics (DFT+ T) and validated the results against experimental ΔHf values obtained through isothermal acid calorimetry. Three structural descriptors were evaluated to develop predictors for ΔHf, finding a strong link between ΔHf and hydrogen bond energy (EHtotal) for neptunyl–hydrogen interactions and total electrostatic attraction energy (Eelectrostatictotal) for neptunyl–cation interactions. Finally, we used Raman spectroscopy together with bond order analysis to probe Np=O bond perturbation due to NCIs. Our results showed a strong correlation between the degree of NCIs by axial oxygen and red-shifting of Np=O symmetrical stretch (ν1) wavenumbers and quantitatively demonstrated that NCIs can weaken the Np=O bond. These properties were then compared to those of related U(VI) and Np(V) phases to evaluate the effects of subtle differences in the NCIs and overall properties. In general, the outcomes of our study demonstrated the role of NCIs in stabilizing actinyl solid materials, which consequently governs their thermochemical behaviors and vibrational signatures.

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Electrostatics

Enthalpy

Noncovalent interactions

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Title: Subtitle: Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties
Creators: Harindu Rajapaksha - University of Iowa
Grant C. Benthin - University of Iowa
Dmytro V. Kravchuk - University of Iowa
Haley Lightfoot - University of Iowa
Sara E. Mason - University of Iowa
Tori Z. Forbes - University of Iowa
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.62(42), pp.17265-17275
DOI: 10.1021/acs.inorgchem.3c02502
PMID: 37816161
PMCID: PMC10598792
NLM abbreviation: Inorg Chem
ISSN: 0020-1669
eISSN: 1520-510X
Publisher: American Chemical Society
Grant note: DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-SC0021420
Language: English
Date published: 10/10/2023
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984476558102771

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