GOLDEN-RULE TREATMENT OF HYDROGEN ABSTRACTION BY PHOTOEXCITED ACRIDINE GUESTS IN FLUORENE SINGLE-CRYSTALS

被引：22

作者：

CHANTRANUPONG, L

WILDMAN, TA

机构：

[1] Department of Chemistry, McMaster University, Hamilton

来源：

JOURNAL OF CHEMICAL PHYSICS | 1991年 / 94卷 / 02期

关键词：

D O I：

10.1063/1.460058

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 kinetics of the photoreduction of acridine guest molecules in fluorene single crystals has been investigated theoretically. The abstraction has been modeled using the golden-rule approach and proceeds by vibrationally assisted tunneling. Parameter values have been taken from experimental data from semiempirical force-field calculations. The calculated temperature and isotope effects are in good agreement with the experimental data for acridine and phenazine guests [B. Prass, J. P. Colpa, and D. Stehlik, J. Chem. Phys. 88, 191 (1988)]. While a fluorene lattice vibration is the likely promoting mode, NH wagging in the radical-pair product plays an essential role.

引用

收藏

页码：1030 / 1033

页数：4

相关论文

共 25 条

[1] VIBRATIONAL ASSIGNMENT OF CARBAZOLE FROM INFRARED RAMAN AND FLUORESCENCE SPECTRA [J].

BREE, A ;

ZWARICH, R .

JOURNAL OF CHEMICAL PHYSICS, 1968, 49 (08) :3344-&

[2] VIBRATIONAL ASSIGNMENT OF FLUORENE FROM INFRARED AND RAMAN SPECTRA [J].

BREE, A ;

ZWARICH, R .

JOURNAL OF CHEMICAL PHYSICS, 1969, 51 (03) :912-&

[3] THE REACTIVE EXCITED-STATES OF ACRIDINE AND PHENAZINE IN SOLUTION - A FLASH-PHOTOLYSIS ELECTRON-SPIN RESONANCE AND CHEMICALLY-INDUCED DYNAMIC ELECTRON POLARIZATION STUDY [J].

BUCKLEY, CD ;

MCLAUCHLAN, KA .

JOURNAL OF PHOTOCHEMISTRY, 1984, 27 (03) :311-316

[4] ABINITIO CALCULATIONS ON THE STRUCTURE OF PYRIDINE IN ITS LOWEST TRIPLET-STATE [J].

BUMA, WJ ;

GROENEN, EJJ ;

VANHEMERT, MC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (14) :5447-5451

[5] AN ELECTRON SPIN-ECHO ENVELOPE MODULATION STUDY OF THE LOWEST TRIPLET-STATE OF PYRIDINE-D5 - SPIN-DENSITY DISTRIBUTION AND STRUCTURE [J].

BUMA, WJ ;

GROENEN, EJJ ;

SCHMIDT, J ;

DEBEER, R .

JOURNAL OF CHEMICAL PHYSICS, 1989, 91 (11) :6549-6565

[6] THE CRYSTAL AND MOLECULAR STRUCTURE OF FLUORENE [J].

BURNS, DM ;

IBALL, J .

PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1955, 227 (1169) :200-214

[7] VIBRATIONALLY ASSISTED TUNNELING IN THE [1,5] SIGMATROPIC HYDROGEN SHIFT IN CIS-1,3-PENTADIENE [J].

CHANTRANUPONG, L ;

WILDMAN, TA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (11) :4151-4154

[8] SYMMETRY CONSIDERATIONS FOR SOLID-STATE PHOTOCHEMICAL HYDROGEN-ABSTRACTION REACTIONS - APPLICATIONS TO FLUORENE DOPED WITH ACRIDINE AND RELATED SYSTEMS [J].

COLPA, JP ;

STEHLIK, D .

CHEMICAL PHYSICS, 1983, 81 (1-2) :163-174

[9] EVIDENCE FOR TUNNELING AS A MECHANISM FOR A PHOTOCHEMICAL HYDROGEN-TRANSFER REACTION IN MOLECULAR-CRYSTALS [J].

COLPA, JP ;

PRASS, B ;

STEHLIK, D .

CHEMICAL PHYSICS LETTERS, 1984, 107 (4-5) :469-474

[10] THE DEVELOPMENT AND USE OF QUANTUM-MECHANICAL MOLECULAR-MODELS .76. AM1 - A NEW GENERAL-PURPOSE QUANTUM-MECHANICAL MOLECULAR-MODEL [J].

DEWAR, MJS ;

ZOEBISCH, EG ;

HEALY, EF ;

STEWART, JJP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (13) :3902-3909