Combination of polarized TIRF and ATR spectroscopies for determination of the second and fourth order parameters of molecular orientation in thin films and construction of an orientation distribution based on the maximum entropy method

Anne F. Runge, Steven S Saavedra, Sergio B. Mendes

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17 Citations (Scopus)

Abstract

This article describes two mathematical formalisms for the determination of the second and fourth order parameters of molecular films using optical spectroscopy. Method A uses polarized total internal reflection fluorescence (TIRF) to calculate the second and fourth order parameters, 〈P 2(cos θ)〉 and 〈P4(cos θ)〉, using an independently determined value for the angle between the absorption and emission dipoles, γ. Method B uses 〈P2(cos θ)〉 obtained from attenuated total reflectance (ATR) data, along with polarized TIRF measurements to calculate 〈P4(cos θ)〉 and (cos2 γ). The choice of a specific method should rely on experimental considerations. We also present a method to separate the contributions of substrate surface roughness and dipole orientation with respect to the molecular axis from the spectroscopically determined second and fourth order parameters. Finally, a maximum entropy approach for construction of an orientation distribution from order parameters is compared with the commonly used delta and Gaussian distributions.

Original languageEnglish (US)
Pages (from-to)6721-6731
Number of pages11
JournalJournal of Physical Chemistry B
Volume110
Issue number13
DOIs
StatePublished - May 6 2006

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Maximum entropy methods
maximum entropy method
Molecular orientation
Fluorescence
Spectroscopy
reflectance
Thin films
fluorescence
thin films
spectroscopy
Gaussian distribution
dipoles
Entropy
Surface roughness
normal density functions
surface roughness
Substrates
entropy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Combination of polarized TIRF and ATR spectroscopies for determination of the second and fourth order parameters of molecular orientation in thin films and construction of an orientation distribution based on the maximum entropy method",
abstract = "This article describes two mathematical formalisms for the determination of the second and fourth order parameters of molecular films using optical spectroscopy. Method A uses polarized total internal reflection fluorescence (TIRF) to calculate the second and fourth order parameters, 〈P 2(cos θ)〉 and 〈P4(cos θ)〉, using an independently determined value for the angle between the absorption and emission dipoles, γ. Method B uses 〈P2(cos θ)〉 obtained from attenuated total reflectance (ATR) data, along with polarized TIRF measurements to calculate 〈P4(cos θ)〉 and (cos2 γ). The choice of a specific method should rely on experimental considerations. We also present a method to separate the contributions of substrate surface roughness and dipole orientation with respect to the molecular axis from the spectroscopically determined second and fourth order parameters. Finally, a maximum entropy approach for construction of an orientation distribution from order parameters is compared with the commonly used delta and Gaussian distributions.",
author = "Runge, {Anne F.} and Saavedra, {Steven S} and Mendes, {Sergio B.}",
year = "2006",
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TY - JOUR

T1 - Combination of polarized TIRF and ATR spectroscopies for determination of the second and fourth order parameters of molecular orientation in thin films and construction of an orientation distribution based on the maximum entropy method

AU - Runge, Anne F.

AU - Saavedra, Steven S

AU - Mendes, Sergio B.

PY - 2006/5/6

Y1 - 2006/5/6

N2 - This article describes two mathematical formalisms for the determination of the second and fourth order parameters of molecular films using optical spectroscopy. Method A uses polarized total internal reflection fluorescence (TIRF) to calculate the second and fourth order parameters, 〈P 2(cos θ)〉 and 〈P4(cos θ)〉, using an independently determined value for the angle between the absorption and emission dipoles, γ. Method B uses 〈P2(cos θ)〉 obtained from attenuated total reflectance (ATR) data, along with polarized TIRF measurements to calculate 〈P4(cos θ)〉 and (cos2 γ). The choice of a specific method should rely on experimental considerations. We also present a method to separate the contributions of substrate surface roughness and dipole orientation with respect to the molecular axis from the spectroscopically determined second and fourth order parameters. Finally, a maximum entropy approach for construction of an orientation distribution from order parameters is compared with the commonly used delta and Gaussian distributions.

AB - This article describes two mathematical formalisms for the determination of the second and fourth order parameters of molecular films using optical spectroscopy. Method A uses polarized total internal reflection fluorescence (TIRF) to calculate the second and fourth order parameters, 〈P 2(cos θ)〉 and 〈P4(cos θ)〉, using an independently determined value for the angle between the absorption and emission dipoles, γ. Method B uses 〈P2(cos θ)〉 obtained from attenuated total reflectance (ATR) data, along with polarized TIRF measurements to calculate 〈P4(cos θ)〉 and (cos2 γ). The choice of a specific method should rely on experimental considerations. We also present a method to separate the contributions of substrate surface roughness and dipole orientation with respect to the molecular axis from the spectroscopically determined second and fourth order parameters. Finally, a maximum entropy approach for construction of an orientation distribution from order parameters is compared with the commonly used delta and Gaussian distributions.

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