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

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: /
Reminder of title:	APPLICATION TO SOME MOLECULAR EXCITED STATES.
Author:	GOLD, JON STUART.
Description:	1 online resource (152 pages)
Notes:	Source: Dissertation Abstracts International, Volume: 48-10, Section: B, page: 2985.
Contained By:	Dissertation Abstracts International48-10B.
Subject:	Physical chemistry. -
Online resource:	click for full text (PQDT)

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. - 1 online resource (152 pages)

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

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

Includes bibliographical references

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.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2018

Mode of access: World Wide Web

Subjects--Topical Terms:

1148725
Physical chemistry.
Index Terms--Genre/Form:

554714
Electronic books.

NANOSECOND TIME RESOLVED CIRCULAR DICHROISM MEASUREMENTS: = APPLICATION TO SOME MOLECULAR EXCITED STATES.
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502 $a Thesis (Ph.D.)--University of California, Santa Cruz, 1987.
504 $a Includes bibliographical references
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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538 $a Mode of access: World Wide Web
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710 2 $a University of California, Santa Cruz. $3 1185267
773 0 $t Dissertation Abstracts International $g 48-10B.
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