Metal-to-metal charge-transfer transitions in Prussian blue hexacyanochromate analogues

David Rogers; Johan Olof Johansson

doi:10.1016/j.mseb.2017.10.003

Metal-to-metal charge-transfer transitions in Prussian blue hexacyanochromate analogues

Research output: Contribution to journal › Article › peer-review

Abstract / Description of output

Time-dependent density functional theory (TD-DFT) calculations are presented for a series of Prussian blue analogues (PBAs) based on hexacyanochromate in order to investigate optical metal-to-metal charge-transfer (MMCT) transitions. PBE0 hybrid DFT calculations at fixed geometry were carried out on binuclear units of (CN)₅-M_A-NC-Cr^III-(CN)₅, with M_A = V^II, V^III, and Cr^II. The MMCT transitions occurred at 743 nm for the V^II-Cr^III PBA and at 780 nm for the V^III-Cr^III PBA. The ordering of the transition energy and strength for these analogues agreed with data available in the literature. The transition for the Cr^II-Cr^III MMCT was found to occur at 284 nm. This study shows that TD-DFT is a powerful method to study optical properties of PBAs and that the results for the relatively simple binuclear cluster are comparable to solid PBAs, where MMCT transitions are typically the dominant feature in the visible part of the absorption spectrum.

Original language	English
Pages (from-to)	28-38
Journal	Materials Science and Engineering: B
Volume	227
Early online date	17 Oct 2017
DOIs	https://doi.org/10.1016/j.mseb.2017.10.003
Publication status	Published - Jan 2018

Keywords / Materials (for Non-textual outputs)

Time-dependent density functional theory
Prussian blue analogues
charge-transfer transitions
multifunctional materials
optical properties

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10.1016/j.mseb.2017.10.003

20171109 Johansson VCrPBAcompResubAccepted author manuscript, 1.35 MBLicence: Creative Commons: Attribution-NonCommercial-NoDerivatives (CC BY-NC-ND)

http://www.sciencedirect.com/science/article/pii/S0921510717302532

Ultrafast Laser Control of Spin Motion in High-Tc Molecule-Based Magnets
Johansson, O.
UK-based charities
1/10/14 → 30/09/19
Project: Research

Cite this

@article{4586989bec22463196b82a34cd241cf2,

title = "Metal-to-metal charge-transfer transitions in Prussian blue hexacyanochromate analogues",

abstract = "Time-dependent density functional theory (TD-DFT) calculations are presented for a series of Prussian blue analogues (PBAs) based on hexacyanochromate in order to investigate optical metal-to-metal charge-transfer (MMCT) transitions. PBE0 hybrid DFT calculations at fixed geometry were carried out on binuclear units of (CN)5-MA-NC-CrIII-(CN)5, with MA = VII, VIII, and CrII. The MMCT transitions occurred at 743 nm for the VII-CrIII PBA and at 780 nm for the VIII-CrIII PBA. The ordering of the transition energy and strength for these analogues agreed with data available in the literature. The transition for the CrII-CrIII MMCT was found to occur at 284 nm. This study shows that TD-DFT is a powerful method to study optical properties of PBAs and that the results for the relatively simple binuclear cluster are comparable to solid PBAs, where MMCT transitions are typically the dominant feature in the visible part of the absorption spectrum. ",

keywords = "Time-dependent density functional theory, Prussian blue analogues, charge-transfer transitions, multifunctional materials, optical properties",

author = "David Rogers and Johansson, {Johan Olof}",

year = "2018",

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doi = "10.1016/j.mseb.2017.10.003",

language = "English",

volume = "227",

pages = "28--38",

journal = "Materials Science and Engineering: B",

issn = "0921-5107",

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T1 - Metal-to-metal charge-transfer transitions in Prussian blue hexacyanochromate analogues

AU - Rogers, David

AU - Johansson, Johan Olof

PY - 2018/1

Y1 - 2018/1

N2 - Time-dependent density functional theory (TD-DFT) calculations are presented for a series of Prussian blue analogues (PBAs) based on hexacyanochromate in order to investigate optical metal-to-metal charge-transfer (MMCT) transitions. PBE0 hybrid DFT calculations at fixed geometry were carried out on binuclear units of (CN)5-MA-NC-CrIII-(CN)5, with MA = VII, VIII, and CrII. The MMCT transitions occurred at 743 nm for the VII-CrIII PBA and at 780 nm for the VIII-CrIII PBA. The ordering of the transition energy and strength for these analogues agreed with data available in the literature. The transition for the CrII-CrIII MMCT was found to occur at 284 nm. This study shows that TD-DFT is a powerful method to study optical properties of PBAs and that the results for the relatively simple binuclear cluster are comparable to solid PBAs, where MMCT transitions are typically the dominant feature in the visible part of the absorption spectrum.

AB - Time-dependent density functional theory (TD-DFT) calculations are presented for a series of Prussian blue analogues (PBAs) based on hexacyanochromate in order to investigate optical metal-to-metal charge-transfer (MMCT) transitions. PBE0 hybrid DFT calculations at fixed geometry were carried out on binuclear units of (CN)5-MA-NC-CrIII-(CN)5, with MA = VII, VIII, and CrII. The MMCT transitions occurred at 743 nm for the VII-CrIII PBA and at 780 nm for the VIII-CrIII PBA. The ordering of the transition energy and strength for these analogues agreed with data available in the literature. The transition for the CrII-CrIII MMCT was found to occur at 284 nm. This study shows that TD-DFT is a powerful method to study optical properties of PBAs and that the results for the relatively simple binuclear cluster are comparable to solid PBAs, where MMCT transitions are typically the dominant feature in the visible part of the absorption spectrum.

KW - Time-dependent density functional theory

KW - Prussian blue analogues

KW - charge-transfer transitions

KW - multifunctional materials

KW - optical properties

U2 - 10.1016/j.mseb.2017.10.003

DO - 10.1016/j.mseb.2017.10.003

M3 - Article

SN - 0921-5107

VL - 227

SP - 28

EP - 38

JO - Materials Science and Engineering: B

JF - Materials Science and Engineering: B

ER -

Metal-to-metal charge-transfer transitions in Prussian blue hexacyanochromate analogues

Abstract / Description of output

Keywords / Materials (for Non-textual outputs)

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Ultrafast Laser Control of Spin Motion in High-Tc Molecule-Based Magnets

Cite this