Nonresonant Photons Catalyze Photodissociation of Phenol

被引：16

作者：

Hilsabeck, Kallie I. ^{[1
]}

Meiser, Jana L. ^{[1
]}

Sneha, Mahima ^{[1
]}

Harrison, John A. ^{[1
,2
]}

Zare, Richard N. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[2] Massey Univ Auckland, Inst Nat & Math Sci, Chem, Auckland 0632, New Zealand

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2019年 / 141卷 / 02期

基金：

美国国家科学基金会;

关键词：

H-ATOM ELIMINATION; DYNAMICS; STATE; MOLECULES; SPECTRA;

D O I：

10.1021/jacs.8b11695

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Phenol represents an ideal polyatomic system for demonstrating photon catalysis because of its large polarizability, well-characterized excited-state potential energy surfaces, and nonadiabatic dissociation dynamics. A non-resonant IR pulse (1064 nm) supplies a strong electric field (4 x 10(7) V/cm) during the photolysis of isolated phenol (C6H5OH) molecules to yield C6H5O + H near two known energetic thresholds: the S-1/S-2 conical intersection and the S-1 - S-0 origin. H-atom speed distributions show marked changes in the relative contributions of dissociative pathways in both cases, compared to the absence of the nonresonant IR pulse. Results indicate that nonresonant photons lower the activation barrier for some pathways relative to others by dynamically Stark shifting the excited-state potential energy surfaces rather than aligning molecules in the strong electric field. Theoretical calculations offer support for the experimental interpretation.

引用

页码：1067 / 1073

页数：7

共 33 条

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