Stability Trend Analysis of Light Lanthanide Complexes with a Fluorophenyl-dipicolinamide: A Quantum Chemical Study

Author:

Wang Bingchun1,Zhang Xinyi1,Li Taotao1,Chen Miaogen1

Affiliation:

1. China Jiliang University

Abstract

Abstract Context Extracting actinides from lanthanides is a crucial step in the reprocessing of spent nuclear fuel, and inevitably the interaction of ligands with lanthanides needs to be considered either. N,N'-diethyl-N,N'-di(para)fluorophenyl-2,6-dipicolinamid (FDPA) has been identified as a promising ligand in lanthanide-actinide separation. In this work, the stability trend of light lanthanide (Ln(III), from La(III) to Eu(III)) complexes with FDPA were theoretically analyzed using density functional theory (DFT). The bond strength, nature of bonding and thermodynamic properties were investigated in an attempt to reveal the affinities for Ln(III). Based on our calculations, the FDPA binds to Ln(III)s via closed-shell interactions. The bond strength for most Ln(III) complexes gradually decreases, which trend consistent with water, making them extractable with little selectivity. Exceptionally, FDPA shows significant selectivity for Ce(III) and Nd(III) due to energetical exclusion.Methods All the DFT calculations were carried out by Gaussian 09 E.01 program suite. The SC-ECP and ECP28MWB-SEG basis sets were used for all the Ln(III)s, and the 6-311g(d,p) basis set was used for other atoms. Vibrational frequency calculations can ensure the structure obtained are minimized on the potential energy surface. The QTAIM parameters were measured by Multiwfn 3.8.

Publisher

Research Square Platform LLC

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3