Resolving Photo-Induced Twisted Intramolecular Charge Transfer with Vibrational Anisotropy and TDDFT | |
Zhang, Wenkai1; Lan, Zhenggang2; Sun, Zheng1; Gaffney, Kelly J.1 | |
刊名 | JOURNAL OF PHYSICAL CHEMISTRY B |
2012-09-20 | |
卷号 | 116期号:37页码:11527-11536 |
中文摘要 | The interplay between reaction environment and photochemical outcome has wide ranging implications for designing and directing light driven chemical conversions. We present a detailed mechanistic description of photoisomerization in julolidine malononitrile (JDMN) as the first step to characterizing this interplay between reaction pathways and reaction environment. We have used polarization resolved UV pump-mid-IR probe spectroscopy and time dependent DFT calculations to investigate the dynamics of charge transfer induced intramolecular rotation in JDMN. We have probed the mechanism and dynamics of photoisomerization with the symmetric and antisymmetric CN-stretch of the malononitrile group. These measurements show the S1 electronic excited state relaxes with a 12.3 ps time constant by isomerizing around both the C-C single and C-C double bond of the malononitrile group with a branching ratio of 1:5. Isomerization around the single bond leads to the formation of a metastable twisted excited state, while isomerization around the double bond leads to excited state quenching via a conical intersection between the S1 and S0 electronic states. We have characterized the electronic and nuclear structure of the long-lived excited state with pump-probe anisotropy measurements and time dependent DFT calculations using the CAM-B3LYP functional and the 6-31G(d,p) basis set. These calculations further confirm that isomerization around the malononitrile single bond forms a twisted intermolecular charge transfer excited state. |
英文摘要 | The interplay between reaction environment and photochemical outcome has wide ranging implications for designing and directing light driven chemical conversions. We present a detailed mechanistic description of photoisomerization in julolidine malononitrile (JDMN) as the first step to characterizing this interplay between reaction pathways and reaction environment. We have used polarization resolved UV pump-mid-IR probe spectroscopy and time dependent DFT calculations to investigate the dynamics of charge transfer induced intramolecular rotation in JDMN. We have probed the mechanism and dynamics of photoisomerization with the symmetric and antisymmetric CN-stretch of the malononitrile group. These measurements show the SI electronic excited state relaxes with a 12.3 Ps time constant by isomerizing around both the C C single and C C double bond of the malononitrile group with a branching ratio of 1:5. Isomerization around the single bond leads to the formation of a metastable twisted excited state, while isomerization around the double bond leads to excited state quenching via a conical intersection between the Si and SO electronic states. We have characterized the electronic and nuclear structure of the long-lived excited state with pump probe anisotropy measurements and time dependent DFT calculations using the CAM-B3LYP functional and the 6-31G(d,p) basis set. These calculations further confirm that isomerization around the malononitrile single bond forms a twisted intermolecular charge transfer excited state. |
学科主题 | 仿真与模拟 |
WOS标题词 | Science & Technology ; Physical Sciences |
类目[WOS] | Chemistry, Physical |
研究领域[WOS] | Chemistry |
关键词[WOS] | MAGNETIC-RESONANCE RELAXATION ; FLUORESCENT MOLECULAR ROTORS ; TEMPERATURE IONIC LIQUIDS ; PHOTOISOMERIZATION DYNAMICS ; STILBENE ISOMERIZATION ; DECAY DYNAMICS ; FREE-VOLUME ; SPECTROSCOPY ; DEPENDENCE ; STATE |
收录类别 | SCI |
语种 | 英语 |
WOS记录号 | WOS:000308855800015 |
公开日期 | 2012-11-12 |
内容类型 | 期刊论文 |
源URL | [http://ir.qibebt.ac.cn:8080/handle/337004/1310] |
专题 | 青岛生物能源与过程研究所_仿真模拟团队 |
作者单位 | 1.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA 2.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao 266101, Shandong, Peoples R China |
推荐引用方式 GB/T 7714 | Zhang, Wenkai,Lan, Zhenggang,Sun, Zheng,et al. Resolving Photo-Induced Twisted Intramolecular Charge Transfer with Vibrational Anisotropy and TDDFT[J]. JOURNAL OF PHYSICAL CHEMISTRY B,2012,116(37):11527-11536. |
APA | Zhang, Wenkai,Lan, Zhenggang,Sun, Zheng,&Gaffney, Kelly J..(2012).Resolving Photo-Induced Twisted Intramolecular Charge Transfer with Vibrational Anisotropy and TDDFT.JOURNAL OF PHYSICAL CHEMISTRY B,116(37),11527-11536. |
MLA | Zhang, Wenkai,et al."Resolving Photo-Induced Twisted Intramolecular Charge Transfer with Vibrational Anisotropy and TDDFT".JOURNAL OF PHYSICAL CHEMISTRY B 116.37(2012):11527-11536. |
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