摘要
获得了I2-1-己烯复合物的吸收横截面和绝对共振拉曼横截面.用约270 nm光激发导致复合物的I—I伸缩振动模和C C伸缩振动模等拉曼基频、泛频及其组合频强度的共振增强.采用含时波包理论的简单模型定量确定I2-1-己烯复合物的光致电子转移振动重组能和均质展宽.总振动重组能3 744 cm-1分布于4个振动模,贡献最大是I—I伸缩振动1ν3,其值为2 490 cm-1,约占总振动重组能的2/3.其次为C C伸缩振动4ν6,其值为1 170 cm-1,约为总振动重组能的1/3.剩余2%的振动重组能是由烷基CH3和CH2的扭转振动3ν6和ν24贡献.
The absorption cross section and absolute resonance Raman cross section at three excitations within ca. 270 nm absorption band of the complex were obtained. Excitation near the maximum of the charge-transfer absorption results in a significant resonance enhancement of fundamentals vI-I and vc=c, and their overtones and combination bands. The reorganization energy in each vibrational mode and homogeneous broadening contribution to the electronic linewidth are determined through quantitative modeling of the absorption and resonance Raman spectra by time-dependent wave-packet theory and using simple model. Total vibrational reorganization energy is measured to be 3 700 cm^-1, which is distributed to four Franck-Condon vibrational modes. The largest contribution is from I-I stretching vibrational mode with reorganization energy 2 490 cm^-1. The second is from C = C stretching vibrational mode with reorganization energy 1 170 cm^-1 . These two vibrational modes possess 98% of the total reorganization energy. The remaining 2% reorganization energy is partitioned into alkyl CH3 and CH2 twist vibration modes of 1-hexene moiety.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2005年第10期1921-1925,共5页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:20273062)
教育部青年教师资助计划(批准号:1918)
浙江省自然科学基金(批准号:201019)
浙江省分析测试基金和浙江理工大学重点实验室建设基金等资助.
关键词
振动重组能
共振拉曼光谱
含时波包理论
电荷转移复合物
Vibrational reorganization energy
Resonance Raman spectroscopy
Time-dependent wave-packet theory
Charge-transfer complex
