Theoretical modeling of the L2,3-edge X-ray absorption spectra of Mn(acac)2 and Co(acac)2 complexes‡

文献信息

发布日期 2015-12-07

DOI 10.1039/C5CP06844D

影响因子 3.676

作者

Silvia Carlotto, Mauro Sambi, Andrea Vittadini

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摘要

Mn(acac)2 (I) and Co(acac)2 (II) L2,3-edge absorption spectra have been modeled using the DFT/ROCIS method. In addition to the agreement between experiment and theory, the combined use of the B3LYP exchange–correlation functional and the def2-TZVP(-f) basis set provided useful information about the coordinative geometry around the M(II) ions as well as about the nature and the strength of the Mn–O and Co–O interaction. The lower excitation energy (EE) side of both I/IIL3 and I/IIL2 intensity distributions mainly includes states having ground state spin multiplicity (S = 5/2 in I and S = 3/2 in II), whereas states with lower spin multiplicity (S = 3/2 in I and S = 1/2 in II) significantly contribute to the higher EE side of both I/IIL3 and I/IIL2. Hence, the occurrence of states involving metal to ligand charge transfer transitions in the presence of ligands with low lying empty π* orbitals on the L3 and L2 higher EE sides is herein confirmed.

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来源期刊

Physical Chemistry Chemical Physics

CiteScore: 5.5

自引率: 10.3%

年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.