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Cu(II)-porphyrin molecular dynamics as seen in novel EPR/stochastic Liouville equation study

Cu(II)-porphyrin molecular dynamics as seen in novel EPR/stochastic Liouville equation study
Cu(II)-porphyrin molecular dynamics as seen in novel EPR/stochastic Liouville equation study
Copper porphyrin dissolved in CH2Cl2:Toluene as fluid and frozen solution was studied as a function of temperature with X-band electron paramagnetic resonance (EPR). Quantitative interpretation was obtained with a recently developed Stochastic Liouville simulation method. For the first time we address the large spin system that translates into a 400 000 dimensional Liouville equation solved under slow-motion conditions. With a simple three parameter microscopic model, the temperature dependence of porphyrin rotational correlation time is determined to be in the range 1 ? 10ns and a fast local motion is in the sub pico-second regime with an amplitude increasing with temperature. The methodology provides an important tool for arriving at an accurate set of spin Hamiltonian parameters since determining a unique set of parameters from a frozen solution EPR experiment is often difficult. Thus the proposed method discriminates between parameters proposed from frozen solution EPR experiment or quantum chemistry calculations. The methodology presented is expected to be valuable in obtaining molecular dynamics picture of metal proteins using EPR as well as in the study of artificial photosynthetic systems.
1463-9076
10930-10941
Hakansson, Par
814e08b5-ae95-408f-a669-bec9c0ef4235
Nguyen, ThaoNguyen
b283dfdc-1b31-4bf8-a3d8-da4045479920
Nair, Prasanth B
d4d61705-bc97-478e-9e11-bcef6683afe7
Edge, Ruth
4020c23f-6101-48da-ab31-c87b8b777605
Stulz, Eugen
9a6c04cf-32ca-442b-9281-bbf3d23c622d
Hakansson, Par
814e08b5-ae95-408f-a669-bec9c0ef4235
Nguyen, ThaoNguyen
b283dfdc-1b31-4bf8-a3d8-da4045479920
Nair, Prasanth B
d4d61705-bc97-478e-9e11-bcef6683afe7
Edge, Ruth
4020c23f-6101-48da-ab31-c87b8b777605
Stulz, Eugen
9a6c04cf-32ca-442b-9281-bbf3d23c622d

Hakansson, Par, Nguyen, ThaoNguyen, Nair, Prasanth B, Edge, Ruth and Stulz, Eugen (2013) Cu(II)-porphyrin molecular dynamics as seen in novel EPR/stochastic Liouville equation study. Physical Chemistry Chemical Physics, 15 (26), 10930-10941. (doi:10.1039/C3CP50788B).

Record type: Article

Abstract

Copper porphyrin dissolved in CH2Cl2:Toluene as fluid and frozen solution was studied as a function of temperature with X-band electron paramagnetic resonance (EPR). Quantitative interpretation was obtained with a recently developed Stochastic Liouville simulation method. For the first time we address the large spin system that translates into a 400 000 dimensional Liouville equation solved under slow-motion conditions. With a simple three parameter microscopic model, the temperature dependence of porphyrin rotational correlation time is determined to be in the range 1 ? 10ns and a fast local motion is in the sub pico-second regime with an amplitude increasing with temperature. The methodology provides an important tool for arriving at an accurate set of spin Hamiltonian parameters since determining a unique set of parameters from a frozen solution EPR experiment is often difficult. Thus the proposed method discriminates between parameters proposed from frozen solution EPR experiment or quantum chemistry calculations. The methodology presented is expected to be valuable in obtaining molecular dynamics picture of metal proteins using EPR as well as in the study of artificial photosynthetic systems.

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e-pub ahead of print date: 24 April 2013
Published date: 14 July 2013
Organisations: Chemistry

Identifiers

Local EPrints ID: 352147
URI: http://eprints.soton.ac.uk/id/eprint/352147
ISSN: 1463-9076
PURE UUID: af784417-acfd-4dc8-a3c3-584d5ed1be69
ORCID for Eugen Stulz: ORCID iD orcid.org/0000-0002-5302-2276

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Date deposited: 07 May 2013 11:18
Last modified: 29 Oct 2019 01:48

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Contributors

Author: Par Hakansson
Author: ThaoNguyen Nguyen
Author: Prasanth B Nair
Author: Ruth Edge
Author: Eugen Stulz ORCID iD

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