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NANOSECOND TIME RESOLVED CIRCULAR DI...

GOLD, JON STUART.

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NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: APPLICATION TO SOME MOLECULAR EXCITED STATES.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: APPLICATION TO SOME MOLECULAR EXCITED STATES./
作者:	GOLD, JON STUART.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 1987,
面頁冊數:	152 p.
附註:	Source: Dissertation Abstracts International, Volume: 48-10, Section: B, page: 2985.
Contained By:	Dissertation Abstracts International48-10B.
標題:	Physical chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=8728161

NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: APPLICATION TO SOME MOLECULAR EXCITED STATES.
GOLD, JON STUART.

NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: APPLICATION TO SOME MOLECULAR EXCITED STATES. - Ann Arbor : ProQuest Dissertations & Theses, 1987 - 152 p.

Source: Dissertation Abstracts International, Volume: 48-10, Section: B, page: 2985.

Thesis (Ph.D.)--University of California, Santa Cruz, 1987.

The previously described technique for observing circular dichroism (CD) on the nanosecond time scale (J. W. Lewis, R. F. Tilton, C. M. Einterz, S. J. Milder, I. D. Kuntz and D. S. Kliger, J. Phys. Chem. 89, 289 (1985)) was extended to obtain the first time resolved CD spectra of some molecular excited states. The CD spectra of the lowest excited states of Ru(bpy)$\sb{3}\sp{2+}$, Cr(bpy)$\sb{3}\sp{3+}$ and Fe(bpy)$\sb{3}\sp{2+}$ were obtained and analyzed. Results for Ru(bpy)$\sb{3}\sp{2+}$ support a single ligand localized description of the transferred electron in the MLCT state. In addition, Ru(bpy)$\sb{3}\sp{2+}$ was electrochemically reduced and the CD spectra of the reduction products were studied using conventional means. The CD spectrum of the singly reduced complex was found to be very similar to the excited state CD spectrum of Ru(bpy)$\sb{3}\sp{2+}$, indicating that the added electron is also single ligand localized. The temperature and time dependence of the excited state absorption of Ru(bpy)$\sb{3}\sp{2+}$ was also studied. These results suggest that there is no dependence of the localized nature of the transferred electron with temperature. Results for Fe(bpy)$\sb{3}\sp{2+}$ indicate that the excited state ligand transitions are very similar in both the ground and excited states as would be expected for a metal centered state. The observed slight red shifting of the ligand transitions in the excited state relative to the ground state is explained by a blue shifting of the MLCT transition in the excited state. The excited state absorption and CD spectra of Cr(bpy)$\sb{3}\sp{3+}$ were also obtained. Spectral assignments are made and discussed in terms of the relative shifting of the observed transitions in the ground and excited states. An overview of CD spectroscopy and of the transient CD technique is presented, as well as a brief discussion of the theoretical basis for the experiments and the interpretations of the results.Subjects--Topical Terms:

1981412
Physical chemistry.

NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: APPLICATION TO SOME MOLECULAR EXCITED STATES.
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245 1 0 $a NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: APPLICATION TO SOME MOLECULAR EXCITED STATES.
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500 $a Source: Dissertation Abstracts International, Volume: 48-10, Section: B, page: 2985.
502 $a Thesis (Ph.D.)--University of California, Santa Cruz, 1987.
520 $a The previously described technique for observing circular dichroism (CD) on the nanosecond time scale (J. W. Lewis, R. F. Tilton, C. M. Einterz, S. J. Milder, I. D. Kuntz and D. S. Kliger, J. Phys. Chem. 89, 289 (1985)) was extended to obtain the first time resolved CD spectra of some molecular excited states. The CD spectra of the lowest excited states of Ru(bpy)$\sb{3}\sp{2+}$, Cr(bpy)$\sb{3}\sp{3+}$ and Fe(bpy)$\sb{3}\sp{2+}$ were obtained and analyzed. Results for Ru(bpy)$\sb{3}\sp{2+}$ support a single ligand localized description of the transferred electron in the MLCT state. In addition, Ru(bpy)$\sb{3}\sp{2+}$ was electrochemically reduced and the CD spectra of the reduction products were studied using conventional means. The CD spectrum of the singly reduced complex was found to be very similar to the excited state CD spectrum of Ru(bpy)$\sb{3}\sp{2+}$, indicating that the added electron is also single ligand localized. The temperature and time dependence of the excited state absorption of Ru(bpy)$\sb{3}\sp{2+}$ was also studied. These results suggest that there is no dependence of the localized nature of the transferred electron with temperature. Results for Fe(bpy)$\sb{3}\sp{2+}$ indicate that the excited state ligand transitions are very similar in both the ground and excited states as would be expected for a metal centered state. The observed slight red shifting of the ligand transitions in the excited state relative to the ground state is explained by a blue shifting of the MLCT transition in the excited state. The excited state absorption and CD spectra of Cr(bpy)$\sb{3}\sp{3+}$ were also obtained. Spectral assignments are made and discussed in terms of the relative shifting of the observed transitions in the ground and excited states. An overview of CD spectroscopy and of the transient CD technique is presented, as well as a brief discussion of the theoretical basis for the experiments and the interpretations of the results.
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