Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions

Due to the enormous threat of protactinium to the environment and human health, its disposal and chemistry have long been important topics in nuclear science. [PaO(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup> is proposed as the predominant species in hydrous and acid...

Full description

Bibliographic Details
Main Authors: Jun Ma, Chuting Yang, Jun Han, Jie Yu, Sheng Hu, Haizhu Yu, Xinggui Long
Format: Article
Language:English
Published: MDPI AG 2019-03-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/24/6/1169
id doaj-414b37e652974ca29cbc3932f9533a31
record_format Article
spelling doaj-414b37e652974ca29cbc3932f9533a312020-11-24T22:10:57ZengMDPI AGMolecules1420-30492019-03-01246116910.3390/molecules24061169molecules24061169Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous SolutionsJun Ma0Chuting Yang1Jun Han2Jie Yu3Sheng Hu4Haizhu Yu5Xinggui Long6Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, Sichuan, ChinaInstitute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, Sichuan, ChinaInstitute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, Sichuan, ChinaDepartment of Chemistry and Center for Atomic Engineering of Advanced Materials, Anhui University, Hefei 230601, ChinaInstitute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, Sichuan, ChinaDepartment of Chemistry and Center for Atomic Engineering of Advanced Materials, Anhui University, Hefei 230601, ChinaInstitute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, Sichuan, ChinaDue to the enormous threat of protactinium to the environment and human health, its disposal and chemistry have long been important topics in nuclear science. [PaO(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup> is proposed as the predominant species in hydrous and acidic solutions, but little is known about its formation mechanism. In this study, density functional theory (DFT) calculations demonstrate a water coordination-proton transfer-water dissociation mechanism for the formation of PaO<sup>3+</sup> in hydrous solutions. First, Pa(V) ion preferentially forms hydrated complexes with a coordination number of 10. Through hydrogen bonding, water molecules in the second coordination sphere easily capture two protons on the same coordinated H<sub>2</sub>O ligand to form [PaO(H<sub>2</sub>O)<sub>9</sub>]<sup>3+</sup>. Water dissociation then occurs to generate the final [PaO(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup>, which is the thermodynamic product of Pa(V) in hydrous solutions.https://www.mdpi.com/1420-3049/24/6/1169Pa(V)hydrous solutionsdensity functional theory (DFT)mechanism
collection DOAJ
language English
format Article
sources DOAJ
author Jun Ma
Chuting Yang
Jun Han
Jie Yu
Sheng Hu
Haizhu Yu
Xinggui Long
spellingShingle Jun Ma
Chuting Yang
Jun Han
Jie Yu
Sheng Hu
Haizhu Yu
Xinggui Long
Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions
Molecules
Pa(V)
hydrous solutions
density functional theory (DFT)
mechanism
author_facet Jun Ma
Chuting Yang
Jun Han
Jie Yu
Sheng Hu
Haizhu Yu
Xinggui Long
author_sort Jun Ma
title Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions
title_short Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions
title_full Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions
title_fullStr Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions
title_full_unstemmed Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions
title_sort density functional theory investigations on the mechanism of formation of pa(v) ion in hydrous solutions
publisher MDPI AG
series Molecules
issn 1420-3049
publishDate 2019-03-01
description Due to the enormous threat of protactinium to the environment and human health, its disposal and chemistry have long been important topics in nuclear science. [PaO(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup> is proposed as the predominant species in hydrous and acidic solutions, but little is known about its formation mechanism. In this study, density functional theory (DFT) calculations demonstrate a water coordination-proton transfer-water dissociation mechanism for the formation of PaO<sup>3+</sup> in hydrous solutions. First, Pa(V) ion preferentially forms hydrated complexes with a coordination number of 10. Through hydrogen bonding, water molecules in the second coordination sphere easily capture two protons on the same coordinated H<sub>2</sub>O ligand to form [PaO(H<sub>2</sub>O)<sub>9</sub>]<sup>3+</sup>. Water dissociation then occurs to generate the final [PaO(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup>, which is the thermodynamic product of Pa(V) in hydrous solutions.
topic Pa(V)
hydrous solutions
density functional theory (DFT)
mechanism
url https://www.mdpi.com/1420-3049/24/6/1169
work_keys_str_mv AT junma densityfunctionaltheoryinvestigationsonthemechanismofformationofpavioninhydroussolutions
AT chutingyang densityfunctionaltheoryinvestigationsonthemechanismofformationofpavioninhydroussolutions
AT junhan densityfunctionaltheoryinvestigationsonthemechanismofformationofpavioninhydroussolutions
AT jieyu densityfunctionaltheoryinvestigationsonthemechanismofformationofpavioninhydroussolutions
AT shenghu densityfunctionaltheoryinvestigationsonthemechanismofformationofpavioninhydroussolutions
AT haizhuyu densityfunctionaltheoryinvestigationsonthemechanismofformationofpavioninhydroussolutions
AT xingguilong densityfunctionaltheoryinvestigationsonthemechanismofformationofpavioninhydroussolutions
_version_ 1725806295352606720