Vibrational spectrum of the spin crossover complex [Fe(phen)2(NCS)2] studied by IR and Raman spectroscopy, nuclear inelastic scattering and DFT calculations

文献信息

发布日期 2006-09-25
DOI 10.1039/B610634J
影响因子 3.676
作者

Kate L. Ronayne, Hauke Paulsen, Andreas Höfer, Andrew C. Dennis, Aleksandr I. Chumakov, Volker Schünemann, Heiner Winkler, Hartmut Spiering, Azzedine Bousseksou, Philipp Gütlich, Alfred X. Trautwein, John J. McGarvey


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摘要

The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)2(NCS)2] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, ΔSvib, which is—together with the electronic entropy difference ΔSel—the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (ΔSvib = 57–70 J mol−1 K−1, depending on the method) is in qualitative agreement with experimental values (20–36 J mol−1 K−1). Only the low energy vibrational modes (20% of the 147 modes of the free molecule) contribute to the entropy difference and about three quarters of the vibrational entropy difference are due to the 15 modes of the central FeN6 octahedron.

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Physical Chemistry Chemical Physics

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.

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