Unusual magnetic properties of mixed-valence system:   Multiconfigurational method theoretical study on Mn-2(+) cation

doi:10.1063/1.2047551

CORC > 北京大学 > 化学与分子工程学院

	Unusual magnetic properties of mixed-valence system: Multiconfigurational method theoretical study on Mn-2(+) cation
	Wang, BW ; Chen, ZD
刊名	journal of chemical physics
	2005
关键词	2ND-ORDER PERTURBATION-THEORY TRANSITION-METAL DIATOMICS RARE-GAS MATRICES DISSOCIATION-ENERGY MANGANESE DIMER CLUSTER IONS MOLECULE PHOTODISSOCIATION SPECTROSCOPY CRMN
DOI	10.1063/1.2047551
英文摘要	The geometry structure, dissociation energy, vibrational frequencies, and low-lying spin-state energy spectrum of Mn-2(+) are investigated by using ab initio CASSCF/ECP10MDF, complete active space self-consistent field/atomic natural orbital basis sets (CASSCF/ANO-s), CASPT2/ECP10MDF, and second-order perturbation theory with CASSCF reference function/atomic natural orbital basis sets (CASPT2/ANO-s) levels of theory. For the ground state the dissociation energy of 1.397 eV calculated at the CASPT2/ANO-s level supports Jarrlod's experimental value of 1.39 eV. The equilibrium bond length and vibrational frequency are 2.940 A calculated at the CASPT2/ANO-s level of theory and 214.4 cm(-1) calculated at the CASSCF/ANO-s level of theory, respectively. On the basis of the mixed-valence model, the Heisenberg exchange constant J(-71.2 cm(-1)) and the double-exchange constant B(647.7 cm(-1)) are extracted explicitly from the low-lying energy spectrum calculated at the higher levels of theory. The magnetic competition between the weaker Heisenberg exchange interactions and the stronger double-exchange interactions makes the ground state a (12)Sigma(g)(+) state, consistent with electron paramagnetic resonance experimental observation, which explains unusual magnetic properties of Mn-2(+), quite different from the antiferromagnetic ground state of Mn-2 and Cr-2. On the other hand, the results calculated at the higher levels of theory show the consistent antiferromagnetic Heisenberg exchange interactions between 3d-3d for Cr-2, Mn-2(+), and Mn-2 (c) 2005 American Institute of Physics.; Physics, Atomic, Molecular & Chemical; SCI(E); EI; PubMed; 5; ARTICLE; 13; 134306; 123
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/199066]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, BW,Chen, ZD. Unusual magnetic properties of mixed-valence system: Multiconfigurational method theoretical study on Mn-2(+) cation[J]. journal of chemical physics,2005.
APA	Wang, BW,&Chen, ZD.(2005).Unusual magnetic properties of mixed-valence system: Multiconfigurational method theoretical study on Mn-2(+) cation.journal of chemical physics.
MLA	Wang, BW,et al."Unusual magnetic properties of mixed-valence system: Multiconfigurational method theoretical study on Mn-2(+) cation".journal of chemical physics (2005).