Femtosecond Photolysis of HOCl(aq): Dissipation of Fragment Kinetic Energy

D. Madsen; C. L. Thomsen; J. Aa. Poulsen; S. J. Knak Jensen; J. Thogersen; S. R. Keiding; E. B. Krissinel

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Femtosecond Photolysis of HOCl(aq): Dissipation of Fragment Kinetic Energy

机译：飞秒HOCl（aq）的光解：碎片动能的耗散

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In this work, we present an experimental study of the energy dependence of the photolysis of aqueous HOCl and the subsequent recombination of the OH and Cl photofragments. Using femtosecond transient absorption spectroscopy, we follow the time-dependent concentration of the fragments. The excess energy in the photolysis is given to the fragments as kinetic energy, and tuning the wavelength enables a study of the energy-dependent thermalization and geminate recombination of the fragments in the liquid environment. The recombination yield and rate are governed by the initial fragment separation, and we deduce an approximately linear dependence of the fragment separation versus the kinetic energy with a slope of 0.13 nm/eV. Performing a simple MD simulation of the system gives qualitative agreement with the observations, although the calculated slope is only 0.04 nm/eV.

机译：在这项工作中，我们提出了对HOCl水溶液的光解以及随后的OH和Cl光碎片重组的能量依赖性的实验研究。使用飞秒瞬态吸收光谱法，我们观察了碎片的时间依赖性浓度。光解中的多余能量以动能的形式分配给碎片，调节波长可以研究液体环境中碎片的能量依赖型热化和萌芽重组。重组产率和速率受初始片段分离的支配，我们推导出片段分离与动能的线性关系，斜率为0.13 nm / eV。尽管计算出的斜率仅为0.04 nm / eV，但对系统进行简单的MD模拟可以得到与观测值的定性一致性。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2003年第19期|共6页
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D. Madsen; C. L. Thomsen; J. Aa. Poulsen; S. J. Knak Jensen; J. Thogersen; S. R. Keiding; E. B. Krissinel;
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正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
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1. Femtosecond Photolysis of HOCl(aq): Dissipation of Fragment Kinetic Energy [J] . D. Madsen, C. L. Thomsen, J. Aa. Poulsen, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2003,第19期

机译：飞秒HOCl（aq）的光解：碎片动能的耗散
2. Kinetic energy analysis of O(~3P_0) and O_2(b ~1#SIGMA#_g~+) fragments produced by photolysis of ozone in the Huggins bands [J] . Patrick OKeeffe, Trevor Ridley, Kenneth P. Lawley, The Journal of Chemical Physics . 1999,第22期

机译：Huggins波段中臭氧光解产生的O（〜3P_0）和O_2（b〜1＃SIGMA＃_g〜+）碎片的动能分析
3. TIME-OF-FLIGHT MEASUREMENTS OF THE KINETIC ENERGIES OF THE O-2(A(1)DELTA(G)) FRAGMENT FROM THE PHOTOLYSIS OF OZONE BETWEEN 287 AND 331 NM [J] . Ball SM., Demoira JCP., Sadowski CM., Chemical Physics Letters . 1995,第1期

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4. Femtosecond Photolysis Of C10/sub2/ (aq) [C] . Thagersen, J., Thomsen, . 2001

机译：飞秒C10 / sub2 /（aq）的光解
5. Thermodynamics and kinetics of the CuCl(aq)/HCl(aq) electrolyzer for hydrogen production. [D] . Hall, Derek M. 2015

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6. Altered Right Ventricular Kinetic Energy Work Density and Viscous Energy Dissipation in Patients with Pulmonary Arterial Hypertension: A Pilot Study Using 4D Flow MRI [O] . Q. Joyce Han, Walter R. T. Witschey, Christopher M. Fang-Yen, -1

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7. Kinetic energy analysis of O(P-3(0)) and O-2(b(1)Sigma(+)(g)) fragments produced by photolysis of ozone in the Huggins bands [O] . O'Keeffe, P, Ridley, T, Lawley, KP, 1999

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8. REACTION KINETICS OF THE PHOTOLYSIS OF NO-, AND THE SPECTRA AND REACTION KINETICS OF THE FREE RADICALS IN THE PHOTOLYSIS OF THE Cl2-O -CO SYSTEM [R] . Alan Butler Harker 1973

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Femtosecond Photolysis of HOCl(aq): Dissipation of Fragment Kinetic Energy

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