Formation of Cerium and Neodymium Isocyanides in the Reactions of Cyanogen with Ce and Nd Atoms in Argon Matrices

doi:10.1021/acs.jpca.9b06026

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	Formation of Cerium and Neodymium Isocyanides in the Reactions of Cyanogen with Ce and Nd Atoms in Argon Matrices
	Fang, ZT ; Vasiliu, M ; Chen, XT ; Gong, Y ; Andrews, L ; Dixon, DA
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2019
卷号	123 期号:38 页码:8208-8219
关键词	ORDER REGULAR APPROXIMATION ABLATED U ATOMS INFRARED-SPECTRA TRIPLE EXCITATIONS BASIS-SETS CHEMISTRY CYANIDE THORIUM COORDINATION U(NC)(2)
ISSN号	1089-5639
DOI	10.1021/acs.jpca.9b06026
文献子类	期刊论文
英文摘要	Laser ablation of metallic Ce and Nd reacting with cyanogen in excess argon during codeposition at 4 K forms Ce(NC)(x) and Nd(NC)(x) for x = 1-3, which are identified from their matrix infrared spectra using cyanogen substituted with C-13 and N-15. The electronic structure calculations were performed for isocyano and cyano Cd and Nd compounds for up to n = 4. The frequencies were calculated at the density functional theory level with three different functionals as well as correlated molecular orbital theory (MP2) and are consistent with the experimental assignments and the corresponding C-12/C-13 isotopic frequency ratios for the isocyano species. The computed frequencies for the analogous cyanide complexes are significantly higher than those for the isocyano isomers, and they are not observed in the spectra. The high spin isocyano complexes are the lowest energy structures. On the basis of the natural population analysis results, the bonding in (CeNC)-Ce-4 and (NdNC)-Nd-6 is essentially purely ionic with the Ce/Nd in the +I-oxidation state. The bonding for disocyano (Ce-3(NC)(2) and Nd-5(NC)(2)) and triisocyano (Ce-2(NC)(3) and Nd-4(NC)(3)) complexes is still quite ionic with the lanthanide in the +II and +III formal oxidation states, respectively. For Ce-1(NC)(4), the oxidation state is best described as being between +III and +IV. Formation of Nd-5(NC)(4) does not really change the electron configuration on the Nd from that in Nd-4(NC)(3) and the oxidation state on the Nd remains at +III. Although Nd compounds with up to 3 NC- groups have more ionic binding than do the corresponding Ce compounds, Ce(NC)(4) has more ionic binding than does Nd(NC)(4). The ionic nature of isocyano Ce and Nd complexes decreases as the number of isocyano groups increases. The energetics of formation of the isocyano Ce and Nd complexes using cyanogen or CN radicals are calculated to be mostly due to exothermic processes, with the exothermicity decreasing as the number of isocyano groups increases.
语种	英语
内容类型	期刊论文
源URL	[http://ir.sinap.ac.cn/handle/331007/32068]
专题	上海应用物理研究所_中科院上海应用物理研究所2011-2017年
作者单位	1.Chinese Acad Sci, Shanghai Inst Appl Phys, Dept Radiochem, Shanghai 201800, Peoples R China; 2.Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA 3.Univ Alabama, Dept Chem, Box 870336, Tuscaloosa, AL 35487 USA;
推荐引用方式 GB/T 7714	Fang, ZT,Vasiliu, M,Chen, XT,et al. Formation of Cerium and Neodymium Isocyanides in the Reactions of Cyanogen with Ce and Nd Atoms in Argon Matrices[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2019,123(38):8208-8219.
APA	Fang, ZT,Vasiliu, M,Chen, XT,Gong, Y,Andrews, L,&Dixon, DA.(2019).Formation of Cerium and Neodymium Isocyanides in the Reactions of Cyanogen with Ce and Nd Atoms in Argon Matrices.JOURNAL OF PHYSICAL CHEMISTRY A,123(38),8208-8219.
MLA	Fang, ZT,et al."Formation of Cerium and Neodymium Isocyanides in the Reactions of Cyanogen with Ce and Nd Atoms in Argon Matrices".JOURNAL OF PHYSICAL CHEMISTRY A 123.38(2019):8208-8219.