Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties
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 actinylmore »
- Authors:
-
[1];
[2];
[1]
- Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States
- Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States, Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States
- Publication Date:
- Research Org.:
- Univ. of Iowa, Iowa City, IA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
- OSTI Identifier:
- 2008378
- Alternate Identifier(s):
- OSTI ID: 2203504; OSTI ID: 2217094
- Report Number(s):
- BNL-225007-2023-JAAM
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- SC0021420; SC0012704
- Resource Type:
- Published Article
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Name: Inorganic Chemistry Journal Volume: 62 Journal Issue: 42; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; Cations; Electrostatics; Enthalpy; Noncovalent interactions; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Complex metal oxide; Environmental chemistry; Density functional theory; Thermodynamics
Citation Formats
Rajapaksha, Harindu, Benthin, Grant C., Kravchuk, Dmytro V., Lightfoot, Haley, Mason, Sara E., and Forbes, Tori Z. Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties. United States: N. p., 2023.
Web. doi:10.1021/acs.inorgchem.3c02502.
Rajapaksha, Harindu, Benthin, Grant C., Kravchuk, Dmytro V., Lightfoot, Haley, Mason, Sara E., & Forbes, Tori Z. Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties. United States. https://doi.org/10.1021/acs.inorgchem.3c02502
Rajapaksha, Harindu, Benthin, Grant C., Kravchuk, Dmytro V., Lightfoot, Haley, Mason, Sara E., and Forbes, Tori Z. Tue .
"Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties". United States. https://doi.org/10.1021/acs.inorgchem.3c02502.
@article{osti_2008378,
title = {Three-Dimensional Noncovalent Interaction Network within [NpO 2 Cl 4 ] 2– Coordination Compounds: Influence on Thermochemical and Vibrational Properties},
author = {Rajapaksha, Harindu and Benthin, Grant C. and Kravchuk, Dmytro V. and Lightfoot, Haley and Mason, Sara E. and Forbes, Tori Z.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.3c02502},
journal = {Inorganic Chemistry},
number = 42,
volume = 62,
place = {United States},
year = {Tue Oct 10 00:00:00 EDT 2023},
month = {Tue Oct 10 00:00:00 EDT 2023}
}
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