Nature of the Chemical Bond in Transition: Dissection of Radical-Molecule Reactivity

被引：1

作者：

Rypkema, Heather A. ^{[1
]}

Donahue, Neil M. ^{[1
]}

Anderson, James G. ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2012年 / 116卷 / 24期

基金：

美国国家科学基金会;

关键词：

ATOM-TRANSFER REACTIONS; EVOLUTION; MODEL;

D O I：

10.1021/jp212023f

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：

A complete method for quantifying the Born Oppenheimer barriers of radical-molecule abstraction reactions is derived from first principles with the dual objectives of analytical prediction and conceptual understanding. Expanding upon the work of Donahue et al. (J. Phys. Chem. A 1998, 102, 3923-3933) this treatment uses the strategic construction of reactant-like and product-like wave functions to evaluate the coupling between crossing diabatic states. The overall reaction coordinate is evaluated in a modular fashion, whereby each region is analyzed within the context of its governing physics.

引用

页码：6303 / 6311

页数：9

共 18 条

[1]

[Anonymous], FUNDAMENTAL PHYS RAD

[2]

[Anonymous], UNPUB

[3] Multiple excited states in a two-state crossing model: Predicting barrier height evolution for H plus alkene addition reactions [J].

Clarke, JS ;

Rypkema, HA ;

Kroll, JH ;

Donahue, NM ;

Anderson, JG .

JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (19) :4458-4468

[4] Predicting radical-molecule barrier heights: The role of the ionic surface [J].

Donahue, NM ;

Clarke, JS ;

Anderson, JG .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (22) :3923-3933

[5] Reaction barriers: Origin and evolution [J].

Donahue, NM .

CHEMICAL REVIEWS, 2003, 103 (12) :4593-4604

[6] The activated complex in chemical reactions [J].

Eyring, H .

JOURNAL OF CHEMICAL PHYSICS, 1935, 3 (02) :107-115

[7] AN MO-THEORETICAL INTERPRETATION OF NATURE OF CHEMICAL REACTIONS .2. GOVERNING PRINCIPLES [J].

FUKUI, K ;

FUJIMOTO, H .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1969, 42 (12) :3399-+

[8] ACTIVATION ENERGIES FROM BOND ENERGIES .1. HYDROGEN TRANSFER REACTIONS [J].

JOHNSTON, HS ;

PARR, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (17) :2544-&

[9]

Lide D. R., 1996, CRC Handbook of Chemistry and Physics

[10] For the quantum theory of homo-polar valency [J].

London, F. .

ZEITSCHRIFT FUR PHYSIK, 1928, 46 (7-8) :455-477

← 1 2 →