NDLI: High-Spin Nitrene Fine-Structure ESR Spectroscopy in Frozen Rigid Glasses: Exact Analytical Expressions for the Canonical Peaks and A D-Tensor Gradient Method for Line Broadening

Content Provider	Springer Nature Link
Author	Koto, Teruaki Sugisaki, Kenji Sato, Kazubu Shiomi, Daisuke Toyota, Kazuo Itoh, Koichi Wasserman, Edel Lahti, Paul M. Takui, Takeji
Copyright Year	2009
Abstract	In high-spin chemistry, random-orientation fine-structure electron paramagnetic resonance (FS ESR) spectroscopy holds the advantages of the most facile and convenient method to identify high-spin systems. The FS ESR spectroscopy for high spins in frozen rigid glasses has seemingly been well established since the first spin-quintet m-dicarbene and m-dinitrene appeared in 1967. The FS ESR spectra of organic quintet entities generated by photolysis in the 2-methyltetrahydrofuran (2-MTHF) glass, however, have never been fully analyzed due to a peculiar line broadening appearing at many canonical peaks. The line broadening has been a notorious obstacle that masks key FS transitions of many cases in organic glasses or argon matrices. We examine the origin of the line broadening, illustrating the comprehensive spectral analysis for m-dinitrenes and other types of typical quintet-state dinitrenes observed in the 2-MTHF glass. Our new approach to the line broadening analysis invokes both exact analytical solutions for the resonance fields of canonical peaks and a magnetic-parameter gradient method. We have derived the exact analytical expressions for FS canonical peaks for high-spin states, for the first time. A microscopic origin of the line broadening observed for high-spin nitrenes generated by photolysis in rigid glasses is proposed on the basis of quantum chemical calculations of the D-tensor.
Starting Page	703
Ending Page	736
Page Count	34
File Format	PDF
ISSN	09379347
Journal	Applied Magnetic Resonance
Volume Number	37
Issue Number	1-4
e-ISSN	16137507
Language	English
Publisher	Springer Vienna
Publisher Date	2009-11-20
Publisher Place	Vienna
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Organic Chemistry Physical Chemistry Atoms and Molecules in Strong Fields, Laser Matter Interaction Spectroscopy/Spectrometry Solid State Physics
Content Type	Text
Resource Type	Article
Subject	Atomic and Molecular Physics, and Optics

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