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Title: A study on the stability of O{sub 2} on oxometalloporphyrins by the first principles calculations

Abstract

The authors investigated the interaction of oxometalloporphyrins (MO(por))--specifically, MoO(por), WO(por), TiO(por), VO(por), and CrO(por)--with O{sub 2} by using first principles calculations. MoO(por) and WO(por) undergo reactions with O{sub 2}; on the other hand, TiO(por), VO(por), and CrO(por) do not. Next, they compared the interaction of MoO(por) and WO(por) with O{sub 2}. Activation barriers for the reactions of MoO(por) and WO(por) with a side-on O{sub 2} are small. For MoO(por)(O{sub 2}), the activation barrier for the reverse reaction that liberates O{sub 2} is also small; however, that for WO(por)(O{sub 2}) is large. The experimental results that photoirradiation with visible light or heating of Mo {sup VI}O(tmp)(O{sub 2}) regenerates Mo {sup VI}O(tmp) by liberating O{sub 2} while W {sup VI}O(tmp)(O{sub 2}) does not [J. Tachibana, T. Imamura, and Y. Sasaki, Bull. Chem. Soc. Jpn. 71, 363 (1998)] are explained by the difference in activation barriers of the reverse reactions. This means that bonds formed between the W atom and O{sub 2} are stronger than those between the Mo atom and O{sub 2}. The bond strengths can be explained by differences in the energy levels between the highest occupied molecular orbital of MoO(por) and WO(por), which are mainly formed from the a orbitalsmore » of the central metal atom and {pi}{sup *} orbitals of O{sub 2}.« less

Authors:
; ; ; ;  [1];  [2];  [2]
  1. Department of Precision Science and Technology and Applied Physics, Osaka University, Suita, Osaka 565-0871 (Japan)
  2. (Japan)
Publication Date:
OSTI Identifier:
20991269
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 126; Journal Issue: 19; Other Information: DOI: 10.1063/1.2733645; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMICAL BONDS; CHROMIUM COMPOUNDS; ENERGY LEVELS; MOLYBDENUM COMPOUNDS; ORGANOMETALLIC COMPOUNDS; PHOTOCHEMISTRY; PORPHYRINS; REACTION KINETICS; STABILITY; TITANIUM OXIDES; TUNGSTEN COMPOUNDS; VANADIUM OXIDES

Citation Formats

Kubota, Yoshiyuki, Escano, Mary Clare Sison, Dy, Eben Sy, Nakanishi, Hiroshi, Kasai, Hideaki, Power Engineering Research and Development Center, Research and Development Department, Kansai Electric Power Co., Inc., Amagasaki, Hyogo 661-0974, and Department of Precision Science and Technology and Applied Physics, Osaka University, Suita, Osaka 565-0871. A study on the stability of O{sub 2} on oxometalloporphyrins by the first principles calculations. United States: N. p., 2007. Web. doi:10.1063/1.2733645.
Kubota, Yoshiyuki, Escano, Mary Clare Sison, Dy, Eben Sy, Nakanishi, Hiroshi, Kasai, Hideaki, Power Engineering Research and Development Center, Research and Development Department, Kansai Electric Power Co., Inc., Amagasaki, Hyogo 661-0974, & Department of Precision Science and Technology and Applied Physics, Osaka University, Suita, Osaka 565-0871. A study on the stability of O{sub 2} on oxometalloporphyrins by the first principles calculations. United States. doi:10.1063/1.2733645.
Kubota, Yoshiyuki, Escano, Mary Clare Sison, Dy, Eben Sy, Nakanishi, Hiroshi, Kasai, Hideaki, Power Engineering Research and Development Center, Research and Development Department, Kansai Electric Power Co., Inc., Amagasaki, Hyogo 661-0974, and Department of Precision Science and Technology and Applied Physics, Osaka University, Suita, Osaka 565-0871. Mon . "A study on the stability of O{sub 2} on oxometalloporphyrins by the first principles calculations". United States. doi:10.1063/1.2733645.
@article{osti_20991269,
title = {A study on the stability of O{sub 2} on oxometalloporphyrins by the first principles calculations},
author = {Kubota, Yoshiyuki and Escano, Mary Clare Sison and Dy, Eben Sy and Nakanishi, Hiroshi and Kasai, Hideaki and Power Engineering Research and Development Center, Research and Development Department, Kansai Electric Power Co., Inc., Amagasaki, Hyogo 661-0974 and Department of Precision Science and Technology and Applied Physics, Osaka University, Suita, Osaka 565-0871},
abstractNote = {The authors investigated the interaction of oxometalloporphyrins (MO(por))--specifically, MoO(por), WO(por), TiO(por), VO(por), and CrO(por)--with O{sub 2} by using first principles calculations. MoO(por) and WO(por) undergo reactions with O{sub 2}; on the other hand, TiO(por), VO(por), and CrO(por) do not. Next, they compared the interaction of MoO(por) and WO(por) with O{sub 2}. Activation barriers for the reactions of MoO(por) and WO(por) with a side-on O{sub 2} are small. For MoO(por)(O{sub 2}), the activation barrier for the reverse reaction that liberates O{sub 2} is also small; however, that for WO(por)(O{sub 2}) is large. The experimental results that photoirradiation with visible light or heating of Mo {sup VI}O(tmp)(O{sub 2}) regenerates Mo {sup VI}O(tmp) by liberating O{sub 2} while W {sup VI}O(tmp)(O{sub 2}) does not [J. Tachibana, T. Imamura, and Y. Sasaki, Bull. Chem. Soc. Jpn. 71, 363 (1998)] are explained by the difference in activation barriers of the reverse reactions. This means that bonds formed between the W atom and O{sub 2} are stronger than those between the Mo atom and O{sub 2}. The bond strengths can be explained by differences in the energy levels between the highest occupied molecular orbital of MoO(por) and WO(por), which are mainly formed from the a orbitals of the central metal atom and {pi}{sup *} orbitals of O{sub 2}.},
doi = {10.1063/1.2733645},
journal = {Journal of Chemical Physics},
number = 19,
volume = 126,
place = {United States},
year = {Mon May 21 00:00:00 EDT 2007},
month = {Mon May 21 00:00:00 EDT 2007}
}