Aspects of intervalence charge transfer in cyanide-bridged systems: Modulated electric field assessment of distances, polarizability changes, and anticipated first hyperpolarizability characteristics

Fredrick W. Vance, Laba Karki, James K. Reigle, Joseph T Hupp, Mark A Ratner

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Abstract

Electroabsorption studies of the systems (CN)5MII-CN-M′III(NH3) 51- (M = Fe, Ru, Os; M′ = Ru, Os) reveal that the metal-to-metal or intervalence charge-transfer transitions are associated with a change in dipole moment, |Δμ|, ranging from 11 to 17 D. This change corresponds to a charge-transfer distance of ca. one-half to two-thirds of the geometric separation between the donor and acceptor metals. This result has consequences for electron transfer parameters, where electronic coupling energies are now upwardly revised to as high as 3000 cm-1. The result is also pertinent in the context of nonlinear optics, where Δμ can be utilized in a two level model to estimate wavelength-dependent molecular first hyperpolarizabilities. The change in polarizability (Δα) accompanying the optical intervalence transitions varies from -10 to +310 Å3. Comparing the experimental results to a simple two state model suggests that the two state picture is seriously deficient for these systems and that a multitude of available additional states must be included to achieve a quantitative description of the polarizable intervalence excited states of these systems.

Original languageEnglish
Pages (from-to)8320-8324
Number of pages5
JournalJournal of Physical Chemistry A
Volume102
Issue number43
Publication statusPublished - Oct 22 1998

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Cyanides
cyanides
Charge transfer
Metals
charge transfer
Electric fields
electric fields
metals
Nonlinear optics
Optical transitions
Dipole moment
nonlinear optics
optical transition
Excited states
electron transfer
dipole moments
Wavelength
Electrons
estimates
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Aspects of intervalence charge transfer in cyanide-bridged systems: Modulated electric field assessment of distances, polarizability changes, and anticipated first hyperpolarizability characteristics",
abstract = "Electroabsorption studies of the systems (CN)5MII-CN-M′III(NH3) 51- (M = Fe, Ru, Os; M′ = Ru, Os) reveal that the metal-to-metal or intervalence charge-transfer transitions are associated with a change in dipole moment, |Δμ|, ranging from 11 to 17 D. This change corresponds to a charge-transfer distance of ca. one-half to two-thirds of the geometric separation between the donor and acceptor metals. This result has consequences for electron transfer parameters, where electronic coupling energies are now upwardly revised to as high as 3000 cm-1. The result is also pertinent in the context of nonlinear optics, where Δμ can be utilized in a two level model to estimate wavelength-dependent molecular first hyperpolarizabilities. The change in polarizability (Δα) accompanying the optical intervalence transitions varies from -10 to +310 {\AA}3. Comparing the experimental results to a simple two state model suggests that the two state picture is seriously deficient for these systems and that a multitude of available additional states must be included to achieve a quantitative description of the polarizable intervalence excited states of these systems.",
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T2 - Modulated electric field assessment of distances, polarizability changes, and anticipated first hyperpolarizability characteristics

AU - Vance, Fredrick W.

AU - Karki, Laba

AU - Reigle, James K.

AU - Hupp, Joseph T

AU - Ratner, Mark A

PY - 1998/10/22

Y1 - 1998/10/22

N2 - Electroabsorption studies of the systems (CN)5MII-CN-M′III(NH3) 51- (M = Fe, Ru, Os; M′ = Ru, Os) reveal that the metal-to-metal or intervalence charge-transfer transitions are associated with a change in dipole moment, |Δμ|, ranging from 11 to 17 D. This change corresponds to a charge-transfer distance of ca. one-half to two-thirds of the geometric separation between the donor and acceptor metals. This result has consequences for electron transfer parameters, where electronic coupling energies are now upwardly revised to as high as 3000 cm-1. The result is also pertinent in the context of nonlinear optics, where Δμ can be utilized in a two level model to estimate wavelength-dependent molecular first hyperpolarizabilities. The change in polarizability (Δα) accompanying the optical intervalence transitions varies from -10 to +310 Å3. Comparing the experimental results to a simple two state model suggests that the two state picture is seriously deficient for these systems and that a multitude of available additional states must be included to achieve a quantitative description of the polarizable intervalence excited states of these systems.

AB - Electroabsorption studies of the systems (CN)5MII-CN-M′III(NH3) 51- (M = Fe, Ru, Os; M′ = Ru, Os) reveal that the metal-to-metal or intervalence charge-transfer transitions are associated with a change in dipole moment, |Δμ|, ranging from 11 to 17 D. This change corresponds to a charge-transfer distance of ca. one-half to two-thirds of the geometric separation between the donor and acceptor metals. This result has consequences for electron transfer parameters, where electronic coupling energies are now upwardly revised to as high as 3000 cm-1. The result is also pertinent in the context of nonlinear optics, where Δμ can be utilized in a two level model to estimate wavelength-dependent molecular first hyperpolarizabilities. The change in polarizability (Δα) accompanying the optical intervalence transitions varies from -10 to +310 Å3. Comparing the experimental results to a simple two state model suggests that the two state picture is seriously deficient for these systems and that a multitude of available additional states must be included to achieve a quantitative description of the polarizable intervalence excited states of these systems.

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