Resonance raman de-enhancement caused by excited state mixed valence

Xianghuai Wang; Guadalupe Valverde-Aguilar; Michael N. Weaver; Stephen F. Nelsen; Jeffrey I. Zink

doi:10.1021/jp071203d

Resonance raman de-enhancement caused by excited state mixed valence

Xianghuai Wang, Guadalupe Valverde-Aguilar, Michael N. Weaver, Stephen F. Nelsen, Jeffrey I. Zink

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

Resonance Raman and absorption spectra of 9,10-bis(2-tert-butyl-2,3- diazabicyclo[2.2.2]oct-3-yl)-anthracene (2) are measured and analyzed. The contribution of the individual vibrational normal modes to the reorganization energy is investigated. Excited-state mixed valence in this system is analyzed using density functional theory electronic structure calculations. The resonance Raman excitation profiles exhibit a resonance de-enhancement effect around 20725 cm ^-1, but a corresponding feature is not observed in the absorption spectrum. This unusual observation is attributed to the presence of a dipole-forbidden, vibronically allowed component of the split mixed valence excited state. The de-enhancement dip is calculated quantitatively and explained in terms of the real and imaginary components of the polarizabilities of the two overlapping excited states.

Original language	English
Pages (from-to)	5441-5447
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	111
Issue number	25
DOIs	https://doi.org/10.1021/jp071203d
State	Published - 28 Jun 2007
Externally published	Yes

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title = "Resonance raman de-enhancement caused by excited state mixed valence",

abstract = "Resonance Raman and absorption spectra of 9,10-bis(2-tert-butyl-2,3- diazabicyclo[2.2.2]oct-3-yl)-anthracene (2) are measured and analyzed. The contribution of the individual vibrational normal modes to the reorganization energy is investigated. Excited-state mixed valence in this system is analyzed using density functional theory electronic structure calculations. The resonance Raman excitation profiles exhibit a resonance de-enhancement effect around 20725 cm -1, but a corresponding feature is not observed in the absorption spectrum. This unusual observation is attributed to the presence of a dipole-forbidden, vibronically allowed component of the split mixed valence excited state. The de-enhancement dip is calculated quantitatively and explained in terms of the real and imaginary components of the polarizabilities of the two overlapping excited states.",

author = "Xianghuai Wang and Guadalupe Valverde-Aguilar and Weaver, {Michael N.} and Nelsen, {Stephen F.} and Zink, {Jeffrey I.}",

year = "2007",

month = jun,

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doi = "10.1021/jp071203d",

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volume = "111",

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journal = "Journal of Physical Chemistry A",

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TY - JOUR

T1 - Resonance raman de-enhancement caused by excited state mixed valence

AU - Wang, Xianghuai

AU - Valverde-Aguilar, Guadalupe

AU - Weaver, Michael N.

AU - Nelsen, Stephen F.

AU - Zink, Jeffrey I.

PY - 2007/6/28

Y1 - 2007/6/28

N2 - Resonance Raman and absorption spectra of 9,10-bis(2-tert-butyl-2,3- diazabicyclo[2.2.2]oct-3-yl)-anthracene (2) are measured and analyzed. The contribution of the individual vibrational normal modes to the reorganization energy is investigated. Excited-state mixed valence in this system is analyzed using density functional theory electronic structure calculations. The resonance Raman excitation profiles exhibit a resonance de-enhancement effect around 20725 cm -1, but a corresponding feature is not observed in the absorption spectrum. This unusual observation is attributed to the presence of a dipole-forbidden, vibronically allowed component of the split mixed valence excited state. The de-enhancement dip is calculated quantitatively and explained in terms of the real and imaginary components of the polarizabilities of the two overlapping excited states.

AB - Resonance Raman and absorption spectra of 9,10-bis(2-tert-butyl-2,3- diazabicyclo[2.2.2]oct-3-yl)-anthracene (2) are measured and analyzed. The contribution of the individual vibrational normal modes to the reorganization energy is investigated. Excited-state mixed valence in this system is analyzed using density functional theory electronic structure calculations. The resonance Raman excitation profiles exhibit a resonance de-enhancement effect around 20725 cm -1, but a corresponding feature is not observed in the absorption spectrum. This unusual observation is attributed to the presence of a dipole-forbidden, vibronically allowed component of the split mixed valence excited state. The de-enhancement dip is calculated quantitatively and explained in terms of the real and imaginary components of the polarizabilities of the two overlapping excited states.

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U2 - 10.1021/jp071203d

DO - 10.1021/jp071203d

M3 - Artículo

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VL - 111

SP - 5441

EP - 5447

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 25

ER -

Resonance raman de-enhancement caused by excited state mixed valence

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