Density functional theory study on the geometric, electronic and vibrational structures of alkali metal porphyrin complexes

被引：31

作者：

Chen, DM ^{[1
]}

Liu, X ^{[1
]}

He, TJ ^{[1
]}

Liu, FC ^{[1
]}

机构：

[1] Univ Sci & Technol China, Dept Phys Chem, Hefei 230026, Anhui, Peoples R China

来源：

CHEMICAL PHYSICS LETTERS | 2002年 / 361卷 / 1-2期

基金：

中国国家自然科学基金;

关键词：

D O I：

10.1016/S0009-2614(02)00931-4

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 ground-state geometry, electronic structures and vibrational frequencies of alkali metal porphyrin complexes, M2P (M = Li, Na, K), have been studied using B3LYP/6-31G(d) method. The computed structures were compared with the crystallographic data of related compounds. TheNa(2)P and K2P molecules have D-4h symmetry with the two alkali metal atoms locating on the different sides of the porphyrin plane. For Li2P, the energy of D-4h structure is higher than the symmetry broken C-2h structure, but the energy difference is very small. Natural population analysis suggests a significant charge transfer from the alkali metals to the porphyrin ring. The vibrational frequencies of M2P (M = Li, Na, K) were calculated and the results were compared with zinc porphyrin (ZnP). (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：106 / 114

页数：9

共 30 条

[1] ELECTRON CORRELATION IN TETRAPYRROLES - AB-INITIO CALCULATIONS ON PORPHYRIN AND THE TAUTOMERS OF CHLORIN [J].

ALMLOF, J ;

FISCHER, TH ;

GASSMAN, PG ;

GHOSH, A ;

HASER, M .

JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (42) :10964-10970

[2] SYNTHESIS AND CHARACTERIZATION OF LITHIUM, SODIUM, AND POTASSIUM PORPHYRIN COMPLEXES - X-RAY CRYSTAL-STRUCTURES OF LI2(C6H12O2)2TMPP, NA2(THF)4OEP, AND K2(PYRIDINE)4OEP [J].

ARNOLD, J ;

DAWSON, DY ;

HOFFMAN, CG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (07) :2707-2713

[3] NOVEL SYNTHETIC ROUTE TO SCANDIUM PORPHYRIN DERIVATIVES AND THE 1ST STRUCTURALLY CHARACTERIZED METALLOPORPHYRIN-ETA-5-CYCLOPENTADIENYL SANDWICH COMPOUND [J].

ARNOLD, J ;

HOFFMAN, CG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (23) :8620-8621

[4] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[5] NEW LITHIUM PORPHYRIN DERIVATIVES - SYNTHESIS OF LI-2(P)(ET(2)O)(2) (P=TTP, TBPP) AND SOLUTION STRUCTURE OF LI-2(TTP)(ET(2)O)(2) BY LI-7 AND N-15 NMR [J].

BRAND, H ;

CAPRIOTTI, JA ;

ARNOLD, J .

INORGANIC CHEMISTRY, 1994, 33 (19) :4334-4337

[6] FACILE REDUCTION OF A DIALKYL ZIRCONIUM(IV) OCTAETHYLPORPHYRIN (OEP) COMPLEX BY H-2 - CRYSTAL-STRUCTURE AND SPECTROSCOPIC CHARACTERIZATION OF [(OEP)ZRCH2SIME(3)] [J].

BRAND, H ;

ARNOLD, J .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (01) :95-97

[7]

Buchler J.W., 1978, The porphyrins, V1, P390

[8] METAL-COMPLEXES WITH TETRAPYRROLE LIGANDS .58. ZIRCONIUM(IV) AND HAFNIUM(IV) BISPORPHYRINATE DOUBLE DECKERS - SYNTHESIS, SPECTRA, REDOX POTENTIALS, AND STRUCTURE [J].

BUCHLER, JW ;

DECIAN, A ;

FISCHER, J ;

HAMMERSCHMITT, P ;

WEISS, R .

CHEMISCHE BERICHTE, 1991, 124 (05) :1051-1058

[9]

BUCHLER JW, 1988, B SOC CHEM JPN, V41, P71

[10] Resonance Raman spectra and excited-state structure of aggregated tetrakis(4-sulfonatophenyl)porphyrin diacid [J].

Chen, DM ;

He, TJ ;

Cong, DF ;

Zhang, YH ;

Liu, FC .

JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (16) :3981-3988

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