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Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra.

Publication ,  Journal Article
Zheng, L; Polizzi, NF; Dave, AR; Migliore, A; Beratan, DN
Published in: The journal of physical chemistry. A
March 2016

The effectiveness of solar energy capture and conversion materials derives from their ability to absorb light and to transform the excitation energy into energy stored in free carriers or chemical bonds. The Thomas-Reiche-Kuhn (TRK) sum rule mandates that the integrated (electronic) oscillator strength of an absorber equals the total number of electrons in the structure. Typical molecular chromophores place only about 1% of their oscillator strength in the UV-vis window, so individual chromophores operate at about 1% of their theoretical limit. We explore the distribution of oscillator strength as a function of excitation energy to understand this circumstance. To this aim, we use familiar independent-electron model Hamiltonians as well as first-principles electronic structure methods. While model Hamiltonians capture the qualitative electronic spectra associated with π electron chromophores, these Hamiltonians mistakenly focus the oscillator strength in the fewest low-energy transitions. Advanced electronic structure methods, in contrast, spread the oscillator strength over a very wide excitation energy range, including transitions to Rydberg and continuum states, consistent with experiment. Our analysis rationalizes the low oscillator strength in the UV-vis spectral region in molecules, a step toward the goal of oscillator strength manipulation and focusing.

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Published In

The journal of physical chemistry. A

DOI

EISSN

1520-5215

ISSN

1089-5639

Publication Date

March 2016

Volume

120

Issue

11

Start / End Page

1933 / 1943

Related Subject Headings

  • Spectrophotometry, Ultraviolet
  • Solar Energy
  • Models, Theoretical
  • 5102 Atomic, molecular and optical physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)
  • 0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics
 

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Zheng, L., Polizzi, N. F., Dave, A. R., Migliore, A., & Beratan, D. N. (2016). Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra. The Journal of Physical Chemistry. A, 120(11), 1933–1943. https://doi.org/10.1021/acs.jpca.6b00692
Zheng, Lianjun, Nicholas F. Polizzi, Adarsh R. Dave, Agostino Migliore, and David N. Beratan. “Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra.The Journal of Physical Chemistry. A 120, no. 11 (March 2016): 1933–43. https://doi.org/10.1021/acs.jpca.6b00692.
Zheng L, Polizzi NF, Dave AR, Migliore A, Beratan DN. Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra. The journal of physical chemistry A. 2016 Mar;120(11):1933–43.
Zheng, Lianjun, et al. “Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra.The Journal of Physical Chemistry. A, vol. 120, no. 11, Mar. 2016, pp. 1933–43. Epmc, doi:10.1021/acs.jpca.6b00692.
Zheng L, Polizzi NF, Dave AR, Migliore A, Beratan DN. Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra. The journal of physical chemistry A. 2016 Mar;120(11):1933–1943.
Journal cover image

Published In

The journal of physical chemistry. A

DOI

EISSN

1520-5215

ISSN

1089-5639

Publication Date

March 2016

Volume

120

Issue

11

Start / End Page

1933 / 1943

Related Subject Headings

  • Spectrophotometry, Ultraviolet
  • Solar Energy
  • Models, Theoretical
  • 5102 Atomic, molecular and optical physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)
  • 0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics