Effects of Ring Fluorination on the Ultraviolet Photodissociation Dynamics of Phenol

被引:4
|
作者
Cooper, Graham A. [1 ]
Cobbin, Mackenzie R. [1 ]
Ashfold, Michael N. R. [1 ]
机构
[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2020年 / 124卷 / 47期
基金
英国工程与自然科学研究理事会;
关键词
D O I
10.1021/acs.jpca.0c08927
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 dynamics of photoinduced O-H bond fission in five fluorinated phenols (2-fluorophenol, 3-fluorophenol, 2,6-difluorophenol, 3,4,5-trifluorophenol, and pentafluorophenol) have been investigated by H Rydberg atom photofragment translational spectroscopy following excitation at many wavelengths in the range 220 <= lambda <= 275 nm. The presence of multiple fluorine substituents reduces the efficiency of O-H bond fission (by tunneling) from the first excited (1(1) pi pi*) electronic state, whereas all bar the perfluorinated species undergo O-H bond fission when excited at shorter wavelengths (to the 2(1) pi pi*state). As in bare phenol, O-H bond fission is deduced to occur by non-adiabatic coupling at conical intersections between the photoprepared "bright" pi pi* states and the 1(1) pi sigma* potential energy surface. In all cases, the fluorophenoxyl photoproducts are found to be formed in a range of vibrational levels, all of which include an odd number of quanta (typically one) in an out-of-plane (a") vibrational mode; this product vibration is viewed as a legacy of the parent out-ofplane motions that promote non-adiabatic coupling to the dissociative 1(1) pi sigma* potential. The radical products also show activity in inplane vibrations involving coupled (both in- and out-of-phase) C-O and C-F wagging motions, which can be traced to the impulse between the recoiling O and H atoms and, in detail, are sensitive to the presence (or not) of an intramolecular F center dot center dot center dot H-O hydrogen bond. Upper limit values for the O-H bond dissociation energies are reported for all molecules studied apart from pentafluorophenol.
引用
收藏
页码:9698 / 9709
页数:12
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