Excited-state charge transfer dynamics of p-dimethylaminobenzonitrile in quadrupolar solvents

被引：30

作者：

Dorairaj, S ^{[1
]}

Kim, HJ ^{[1
]}

机构：

[1] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2002年 / 106卷 / 10期

关键词：

D O I：

10.1021/jp012991o

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：

Excited-state intramolecular charge transfer of p-dimethylaminobenzonitrile (DMABN) in benzene, toluene, and dioxane is studied. By combining the recent continuum quadrupolar solvent theory of Jeon and Kim [J. Phys. Chem. A 2000, 104, 9812] and the two-dimensional formulation of the DNABN photoreaction in dipolar solvents by Fonseca et al. [J. Mol. Liq. 1994, 60, 161], the influence of both solvent quadrupole reorganization and solute twist on the reaction free energetics and dynamics is accounted for. The solution-phase reaction paths are investigated with the aid of experimental information on the frequencies associated with solute torsional and collective solvent quadrupole dynamics. The rate constants and transmission coefficients are analyzed using transition state theory with the neglect of dissipative dynamics. Our results are in reasonable agreement with the experimental findings in quadrupolar solvents.

引用

页码：2322 / 2327

页数：6

共 50 条

[1]

[Anonymous], 1986, ANGEW CHEM INT EDIT, DOI DOI 10.1002/ANGE.19610732103

[2] INTRAMOLECULAR PHOTOINDUCED CHARGE SEPARATION AND CHARGE RECOMBINATION OF THE PRODUCT ION-PAIR STATES OF A SERIES OF FIXED-DISTANCE DYADS OF PORPHYRINS AND QUINONES - ENERGY-GAP AND TEMPERATURE DEPENDENCES OF THE RATE CONSTANTS [J].

ASAHI, T ;

OHKOHCHI, M ;

MATSUSAKA, R ;

MATAGA, N ;

ZHANG, RP ;

OSUKA, A ;

MARUYAMA, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (13) :5665-5674

[3] COMPARISON OF A VISCOELASTIC THEORY OF SOLVATION DYNAMICS TO TIME-RESOLVED EXPERIMENTS IN A NONPOLAR SOLUTION [J].

BERG, M .

CHEMICAL PHYSICS LETTERS, 1994, 228 (4-5) :317-322

[4] Role of intramolecular torsion and solvent dynamics in the charge-transfer kinetics in triphenylphosphine oxide derivatives and DMABN [J].

Changenet, P ;

Plaza, P ;

Martin, MM ;

Meyer, YH .

JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (44) :8186-8194

[5] PHOTOCHEMISTRY OF CARBOCYANINE ALKYLTRIPHENYLBORATE SALTS - INTRA-ION-PAIR ELECTRON-TRANSFER AND THE CHEMISTRY OF BORANYL RADICALS [J].

CHATTERJEE, S ;

DAVIS, PD ;

GOTTSCHALK, P ;

KURZ, ME ;

SAUERWEIN, B ;

YANG, XQ ;

SCHUSTER, GB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (17) :6329-6338

[6] Excited state structure of 4-(dimethylamino)benzonitrile studied by femtosecond mid-infrared spectroscopy and ab initio calculations [J].

Chudoba, C ;

Kummrow, A ;

Dreyer, J ;

Stenger, J ;

Nibbering, ETJ ;

Elsaesser, T ;

Zachariasse, KA .

CHEMICAL PHYSICS LETTERS, 1999, 309 (5-6) :357-363

[7] Shedding light on excited-state structures by theoretical analysis of femtosecond transient infrared spectra: Intramolecular charge transfer in 4-(dimethylamino)benzonitrile [J].

Dreyer, J ;

Kummrow, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (11) :2577-2585

[8] TWISTED INTRAMOLECULAR CHARGE-TRANSFER DYNAMICS IN POLAR-SOLVENTS [J].

FONSECA, T ;

KIM, HJ ;

HYNES, JT .

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1994, 82 (1-3) :67-79

[9] THE PATH OF CHEMICAL-REACTIONS - THE IRC APPROACH [J].

FUKUI, K .

ACCOUNTS OF CHEMICAL RESEARCH, 1981, 14 (12) :363-368

[10]

GRABOWSKI ZR, 1979, NOUV J CHIM, V3, P443

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