卤代卡宾自由基反应动力学的实验和理论研究
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摘要
本论文报道了我们对卤代卡宾自由基反应动力学的理论和实验研究。论文的第一部分主要是HCF自由基动力学的实验研究：(1)利用激光光解-激光诱导荧光技术对HCF((?)~1A″)与直链烷烃和醇类猝灭动力学的实验研究；(2)利用激光光解-激光诱导荧光技术对HCF((?)~1 A′)与一些小分子反应动力学的实验研究。论文的第二部分报道了我们利用量子化学理论和TST-RRKM理论对六个卡宾自由与NO以及HCF与C_2H_2和C_2H_4反应动力学的理论研究。
激发态HCF((?)~1 A″)自由基猝灭动力学的实验研究：
利用213nm的激光光解CHFBr_2产生HCF自由基，用另一束波长为492.58nm的激光将HCF自由基从电子基态(?)~1 A′(000)态激励到激发态(?)~1 A″(030)态，通过检测处于激发态(?)~1 A″(030)的HCF辐射的时间分辨总包荧光信号，测定了室温下腔体压力为14.0Torr时直链烷烃和醇类分子对HCF((?)~1 A″)自由基的猝灭速率常数，醇类和烷烃分子对HCF((?)~1 A″)自由基的猝灭都是较为有效的，猝灭总包速率常数具有与“刚球碰撞模型”气动截面相当的数量级(10~(-10)cm~3·molec~(-1)·s~(-1))；随着猝灭剂分子中碳原子数的增加，HCF((?)~1 A″)的猝灭速率常数及碰撞猝灭截面也线性增加。利用碰撞络合物模型计算了HCF((?)~1 A″)与直链烷烃和醇类分子的碰撞络合物生成截面并与实验比较，发现计算结果与实验定性吻合。对实验结果与计算数据进行分析讨论，结果表明电子激发态HCF((?)~1 A″)的猝灭过程可能属于多极吸引势起重要作用的入口通道控制机制，HCF((?)~1 A″)对烷烃和醇类C-H键的插入反应在猝灭过程中起着重要作用。
This dissertation presents the experimental and theoretical studies on the reaction kinetics of halocarbenes. The first part is mainly about the experimental studies on the kinetics of HCF
radical: (I) the quenching kinetics of HCF((A|~)~1A") by alcohol and alkane molecules using LP/LIF technique. (2) the reaction kinetics of HCF((X|~)~1A') with some small molecules using LP/LIF technique. The second part is about the theoretical studies on the kinetics of six halocarbenes reaction with NO and HCF reaction with C_2H_2 and C_2H_4 using quantum chemistry methods and TST-RRKM theory.
Time-resolved kinetic study on quenching of HCF((A|~)~1A") using LP/LIF technique:
The HCF radicals were produced by laser photolysis of CHFBr_2 molecules at 213 nm and were then excited from the ground electronic state to (A|~)~1A" state with Nd: YAG laser pumped dye laser at 492.58 nm which is corresponding to the transition of (A|~)~1A"(030)←(X|~)~1A'(000). The quenching rate constants k_q and thermally averaged cross section σ_q for collision quenching of
HCF((A|~)~1A") state by normal alkane and alcohol molecules were measured at room temperature
(298K) by observed the time-resolved fluorescence signals of the excited HCF in a cell at total pressure of about 14.0 Torr. Some regularity of the quenching rate constants with properties of
quenchers was obtained. It was shown that the quenching rate constants of HCF((A|~)~1A") by the quenchers increase almost linearly with the number of C-H bonds contained in the homologous molecules. The formation cross sections σ_(cf) of the complex between HCF((A|~)~1A") and
quenchers were calculated by using collision complex model. The qualitative trendency of σ_(cf) is agreement with that of measured data. The results mean that the collisional quenching rates of HCF((A|~)~1A") is probably controlled by the entranced channel, in which attractive forces via collision complex formation play an important role.
激发态HCF((?)~1 A″)自由基猝灭动力学的实验研究：
利用213nm的激光光解CHFBr_2产生HCF自由基，用另一束波长为492.58nm的激光将HCF自由基从电子基态(?)~1 A′(000)态激励到激发态(?)~1 A″(030)态，通过检测处于激发态(?)~1 A″(030)的HCF辐射的时间分辨总包荧光信号，测定了室温下腔体压力为14.0Torr时直链烷烃和醇类分子对HCF((?)~1 A″)自由基的猝灭速率常数，醇类和烷烃分子对HCF((?)~1 A″)自由基的猝灭都是较为有效的，猝灭总包速率常数具有与“刚球碰撞模型”气动截面相当的数量级(10~(-10)cm~3·molec~(-1)·s~(-1))；随着猝灭剂分子中碳原子数的增加，HCF((?)~1 A″)的猝灭速率常数及碰撞猝灭截面也线性增加。利用碰撞络合物模型计算了HCF((?)~1 A″)与直链烷烃和醇类分子的碰撞络合物生成截面并与实验比较，发现计算结果与实验定性吻合。对实验结果与计算数据进行分析讨论，结果表明电子激发态HCF((?)~1 A″)的猝灭过程可能属于多极吸引势起重要作用的入口通道控制机制，HCF((?)~1 A″)对烷烃和醇类C-H键的插入反应在猝灭过程中起着重要作用。
This dissertation presents the experimental and theoretical studies on the reaction kinetics of halocarbenes. The first part is mainly about the experimental studies on the kinetics of HCF
radical: (I) the quenching kinetics of HCF((A|~)~1A") by alcohol and alkane molecules using LP/LIF technique. (2) the reaction kinetics of HCF((X|~)~1A') with some small molecules using LP/LIF technique. The second part is about the theoretical studies on the kinetics of six halocarbenes reaction with NO and HCF reaction with C_2H_2 and C_2H_4 using quantum chemistry methods and TST-RRKM theory.
Time-resolved kinetic study on quenching of HCF((A|~)~1A") using LP/LIF technique:
The HCF radicals were produced by laser photolysis of CHFBr_2 molecules at 213 nm and were then excited from the ground electronic state to (A|~)~1A" state with Nd: YAG laser pumped dye laser at 492.58 nm which is corresponding to the transition of (A|~)~1A"(030)←(X|~)~1A'(000). The quenching rate constants k_q and thermally averaged cross section σ_q for collision quenching of
HCF((A|~)~1A") state by normal alkane and alcohol molecules were measured at room temperature
(298K) by observed the time-resolved fluorescence signals of the excited HCF in a cell at total pressure of about 14.0 Torr. Some regularity of the quenching rate constants with properties of
quenchers was obtained. It was shown that the quenching rate constants of HCF((A|~)~1A") by the quenchers increase almost linearly with the number of C-H bonds contained in the homologous molecules. The formation cross sections σ_(cf) of the complex between HCF((A|~)~1A") and
quenchers were calculated by using collision complex model. The qualitative trendency of σ_(cf) is agreement with that of measured data. The results mean that the collisional quenching rates of HCF((A|~)~1A") is probably controlled by the entranced channel, in which attractive forces via collision complex formation play an important role.
引文
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