The mechanism of spin polarization in aromatic free radicals

被引：18

作者：

Adamo, C

Barone, V

Subra, R

机构：

[1] Univ Basilicata, Dipartimento Chim, I-85100 Potenza, Italy

[2] Univ Naples, Dipartimento Chim, I-80134 Naples, Italy

[3] Univ Grenoble 1, Etud Dynam & Struct Select Lab, F-38041 Grenoble, France

来源：

THEORETICAL CHEMISTRY ACCOUNTS | 2000年 / 104卷 / 3-4期

关键词：

spin polarization; density functional theory; hyperfine coupling constants;

D O I：

10.1007/s002140000132

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The spin-polarization mechanism in aromatic systems is analyzed with reference to the prototypical phenoxyl. cyclohexadienyl and benzyl radicals. In particular, a decomposition into "first-order'' and "second-order" contributions is proposed, which helps to rationalize the different nature of the spin density for atoms in alpha or in beta positions with respect to the radical center. The different weights of the two contributions are discussed on the basis of Hartree-Fock and density functional computations.

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收藏

页码：207 / 209

页数：3

相关论文

共 17 条

[1] Structure and magnetic properties of benzyl, anilino, and phenoxyl radicals by density functional computations [J].

Adamo, C ;

Subra, R ;

Di Matteo, A ;

Barone, V .

JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (23) :10244-10254

[2]

[Anonymous], 1993, DNA FREE RADICALS

[3] Structure and hyperfine parameters of cyclopropyl and bicyclobutyl radicals from post-Hartree-Fock computations [J].

Barone, V ;

Subra, R .

JOURNAL OF CHEMICAL PHYSICS, 1996, 104 (07) :2630-2637

[4] CONFORMATIONAL BEHAVIOR AND MAGNETIC-PROPERTIES OF ORGANIC RADICALS DERIVED FROM AMINO-ACID-RESIDUES - THE DIPEPTIDE ANALOG OF GLYCINE RADICAL [J].

BARONE, V ;

ADAMO, C ;

GRAND, A ;

BRUNEL, Y ;

FONTECAVE, M ;

SUBRA, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (03) :1083-1089

[5] Electronic structure of the Y-D tyrosyl radical in photosystem II: A high-frequency electron paramagnetic resonance spectroscopic and density functional theoretical study [J].

Farrar, CT ;

Gerfen, GJ ;

Griffin, RG ;

Force, DA ;

Britt, RD .

JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (33) :6634-6641

[6]

Frisch M. J., 1999, GAUSSIAN 98 REVISION

[7]

GILLON B, 1989, MOL PHYSICS CHEM BIO, V2

[8] Electronic structure of the neutral tyrosine radical in frozen solution. Selective H-2-, C-13-, and O-17-isotope labeling and EPR spectroscopy at 9 and 35 GHz [J].

Hulsebosch, RJ ;

vandenBrink, JS ;

Nieuwenhuis, SAM ;

Gast, P ;

Raap, J ;

Lugtenburg, J ;

Hoff, AJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (37) :8685-8694

[9] Structures and spectroscopic characteristics of 5,6-dihydro-6-thymyl and 5,6-dihydro-5-thymyl radicals by an integrated quantum mechanical approach including electronic, vibrational, and solvent effects [J].

Jolibois, F ;

Cadet, J ;

Grand, A ;

Subra, R ;

Rega, N ;

Barone, V .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (08) :1864-1871

[10]

Kahn O, 1993, MOL MAGNETISM