Spectroscopy and dynamics of A [2B1] allyl radical

被引：24

作者：

Castiglioni, Luca ^{[1
]}

Bach, Andreas ^{[1
]}

Chen, Peter ^{[1
]}

机构：

[1] ETH, Organ Chem Lab, CH-8093 Zurich, Switzerland

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2006年 / 8卷 / 22期

关键词：

D O I：

10.1039/b602412b

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 A [B-2(1)] <- X[(2)A(2)] band system between 380 and 420 nm was observed in a supersonic jet expansion. The allyl radical was found to dissociate following electronic excitation, releasing a hydrogen atom. Monitoring the appearance of the hydrogen atom photoproduct as a function of the excitation laser wavelength, similar spectral features are observed as in earlier absorption experiments. Time- and frequency-resolved photoionization of the hydrogen atom product provides information on the unimolecular dissociation dynamics. The measured dissociation rates and kinetic energy releases of both allyl radical, C3H5, and partially deuterated allyl radical, C3DH4, suggest direct loss of the central hydrogen atom, leading to allene as the major product.

引用

收藏

页码：2591 / 2598

页数：8

相关论文

共 53 条

[1] Rotational analysis of the (Å)over-bar2B1 ← (Χ)over-bar2A2 electronic spectrum of the allyl radical [J].

Achkasova, E ;

Araki, M ;

Denisov, A ;

Maier, JP .

MOLECULAR PHYSICS, 2005, 103 (11-12) :1555-1560

[2] The allyl radical revisited: a theoretical study of the electronic spectrum [J].

Aquilante, F ;

Jensen, KP ;

Roos, BO .

CHEMICAL PHYSICS LETTERS, 2003, 380 (5-6) :689-698

[3] Vibrational zero-point energies and thermodynamic functions beyond the harmonic approximation [J].

Barone, V .

JOURNAL OF CHEMICAL PHYSICS, 2004, 120 (07) :3059-3065

[4] Potential energy surface crossings in organic photochemistry [J].

Bernardi, F ;

Olivucci, M ;

Robb, MA .

CHEMICAL SOCIETY REVIEWS, 1996, 25 (05) :321-&

[5] ELECTRONIC-SPECTRUM OF ALLYL AND ALLYL-D5 RADICALS - THE B[1(2)A1][-X[1(2)A2], C[2(2)B1][-X[1(2)A2], AND D[1(2)B2][-X[1(2)A2] BAND SYSTEMS [J].

BLUSH, JA ;

MINSEK, DW ;

CHEN, P .

JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (25) :10150-10154

[6] New generalized gradient approximation functionals [J].

Boese, AD ;

Doltsinis, NL ;

Handy, NC ;

Sprik, M .

JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (04) :1670-1678

[7] ELECTRONIC SPECTRA OF FREE ALLYL RADICAL AND SOME OF ITS SIMPLE DERIVATIVES [J].

CALLEAR, AB ;

LEE, HK .

TRANSACTIONS OF THE FARADAY SOCIETY, 1968, 64 (542P) :308-&

[8] Probing centrifugal barriers in unimolecular dissociation of the allyl radical [J].

Castiglioni, L ;

Bach, A ;

Chen, P .

JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (06) :962-964

[9] ELECTRONIC ABSORPTION SPECTRUM AND DISSOCIATION ENERGY OF ALLYL RADICAL [J].

CURRIE, CL ;

RAMSAY, DA .

JOURNAL OF CHEMICAL PHYSICS, 1966, 45 (02) :488-+

[10] Kinetics and dynamics in the photodissociation of the allyl radical [J].

Deyerl, HJ ;

Gilbert, T ;

Fischer, I ;

Chen, P .

JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (08) :3329-3332

← 1 2 3 4 5 6 →