The Ionization energy of cationic cyanine dyes

Selsby, R. G.; Nelson, R. C.

doi:10.1016/0022-2852(70)90048-2

Cited by 20 publications

(15 citation statements)

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“…Two main effects account for the difference between the calculated values and the measurements on the adsorbed dye: (1) the effect of linear aggregation; and (2) the effect on the IP due to the presence of a polarizable substrate. The former is estimated by Nelson and Yianoulis" at 0.5-0.7 eV, while the latter amounts to 0.33 eV for pinacyanol adsorbed on CdS [46]. Thus, for the IP, the difference between calculated and measured values may be independently estimated at about 1 eV, which agrees with that found above.…”

Section: Application To the Sensitizing Dye Pinacyanolsupporting

confidence: 75%

“…Using a bromine anion polarization correction of 0.13 eV [46] for the IP (the corresponding effect for the EA can be neglected due to a cancelling of terms), one obtains IP, = 6.65 eV and EA, = 2.48 eV. The IP and EA of pinacyanol have been studied for the dye adsorbed on a substrate such as CdS.…”

Section: Application To the Sensitizing Dye Pinacyanolmentioning

confidence: 98%

“…The only modification of the method necessary to treat this ionic material is the inclusion of the integral y d = e2/(d?+0.5Zi? )1'2, which represents the Coulomb repulsion between a 7r electron at site i in the core and the Br-, in the diagonal element of the core Hamiltonian [46]. (di is the distance from Br-to site i.…”

Section: Application To the Sensitizing Dye Pinacyanolmentioning

confidence: 99%

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A semi‐empirical MO theory for ionization potentials and electron affinities. II. Vertical and adiabatic values, benzenoid and nonbenzenoid aromatic hydrocarbons, and conjugated molecules with heteroatoms

Selsby

Grimison

1977

Int J of Quantum Chemistry

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AbstractsFurther developments of a recent semiempirical, variable effective charge MO theory for calculation of ionization potentials (IP) and electron affinities (EA) as energy differences between separately minimized ground and ionized states are reported. The method is extended to adiabatic as well as vertical IPS and EAS by including core repulsion and u bond compression energies in the total energy. The method is generalized to heteroatomic systems and is simplified by neglecting penetration integrals. As before, only two molecular parameters, the vertical IPS of benzene and naphthalene, are required to set the magnitude of the u changes associated with the polarization of the core during loss or gain of a ?r charge. Twenty-seven aromatic molecules are studied, including polyacenes, condensed ring compounds, nonbenzenoids with five and seven member rings, nonplanar molecules, and heteroatomics with N', as in pyridine, N+', as in pyrrole, and Of', as in furan. The results are within 0.2 eV of the photoelectron spectroscopic vertical IPS and the predicted vertical-adiabatic separation is consistent with the shape of the first band. The calculated EAS are within 0.2 eVof the observed values.The calculation is used to predict the IP and EA of the ionic photosensitizing cyanine dye, pinacyanol. The values obtained are consistent with the latest measured IP and EA of the adsorbed dye, corrected for surface and aggregation polarization effects.On presente des dtveloppements nouveaux d'une theorie de type MO semi-empirique avec des charges effectives variables pour calculer des potentiels d'ionisation (IP) et des affinites Clectroniques (EA) comme des difftrences d'tnergie entre les &tats fondamentaux et ionists, minimists stpartment. La mtthode est applicable aux IPS et EAS verticaux et adiabatiques grlce a I'inclusion de la rtpulsion des coeurs et de I'tnergie de compression de la liaison (r dans I'dnergie totale. Elle a Cte gentralisbe pour des systemes heteroatomiques et a e t t simplifite en ntgligeant les inttgrales de ptnttration. Seulement deux paramttres moltculaires, les IPS verticaux du benzene et du naphthalene, sont necessaires pour ttablir la grandeur des changements u associts a la polarisation du meur lors de la perte ou du gain d'une charge R. On a ttudit 27 molCcules aromatiques, y i n c h des polyact.nes, des composes annulaires condenses, des nonbenztnoides avec des anneaux de cinq et sept membres, des molecules non-planaires et des composts htteroatomiques avec N', mmme dans la pyridine, N'*, comme dans le pyrrole, et O", comme dans le furan. Les rtsultats different de moins de 0.2 eVdes IPS verticaux obtenus de la spectroscopie Clectronique. La stparation vertical-adiabatique est compatible avec la forme de la premiere bande. Les EAS calculees different de moins de 0.2 eV des valeurs observtes. Le calcul a t t e utilist pour prtdire I'IP et I'EA du colorant pinacyanole. Les valeurs obtenues sont en accord avec les valeurs mesurtes les plus recentes du colorant adsorbt, corrigtes pour tenir com...

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Section: Application To the Sensitizing Dye Pinacyanolsupporting

confidence: 75%

Section: Application To the Sensitizing Dye Pinacyanolmentioning

confidence: 98%

Section: Application To the Sensitizing Dye Pinacyanolmentioning

confidence: 99%

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A semi‐empirical MO theory for ionization potentials and electron affinities. II. Vertical and adiabatic values, benzenoid and nonbenzenoid aromatic hydrocarbons, and conjugated molecules with heteroatoms

Selsby

Grimison

1977

Int J of Quantum Chemistry

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“…Attempts have been made [9,10] to correlate this quantity to experimental single molecule EAs with considerable success. It is evident that we cannot use these simple methods ; instead we shall use the HoyiandGoodman corrections [11,12]. After electron capture, there is a change in the electronic charge density and the screening of the a electrons.…”

Section: The Electron Affinity For a Single Dye Moleculementioning

confidence: 99%

“…We have taken all the C-C distances to be 1.40 A, and the C-N, 1.33 A. For the single molecule the counterion is placed at X= 0.0, Y= -3.8 ~, consistent with both the electrostatic interactions with the cation charge density and the van der Waals radii [12,18].…”

Section: Calculationsmentioning

confidence: 99%

Electron affinity of adsorbed dye monolayers

Yianoulis

Nelson

1982

Molecular Physics

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We have calculated the electron affinity of dye molecules and compared it with experimental results from the electron beam retardation method. The calculations were performed on the dye pinacyanol adsorbed on CdS. First, we calculated the single molecule electron affinity which corresponds to the vapour state electron affinity. Next, we calculated the electron affinity of a molecule in a linear aggregate, considering the neighbouring molecules, and finally, the electron affinity of molecules in aggregates adsorbed on an ideal crystal substrate and on a substrate with defects. We prove that there is a distribution of electron affinities which is caused by random defects on the substrate surface. The experimental electron affinity for monolayers of pinacyanol on CdS corresponds to the highest electron affinities in the distribution. We propose that this is caused by electron diffusion in the dye, and present additional experimental evidence which supports our conclusion. The effects of various interactions are evaluated ; these are nearly independent of the SCF-LCAO method used, since they are found by taking the difference of two calculations. These results are compared with the corresponding ionization energies, which have been verified by photoionization expdriments.

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Chemical Sensitization, Spectral Sensitization, and Latent Image Formation in Silver Halide Photography

James¹

1986

Advances in Photochemistry

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The Ionization energy of cationic cyanine dyes

Cited by 20 publications

References 19 publications

A semi‐empirical MO theory for ionization potentials and electron affinities. II. Vertical and adiabatic values, benzenoid and nonbenzenoid aromatic hydrocarbons, and conjugated molecules with heteroatoms

A semi‐empirical MO theory for ionization potentials and electron affinities. II. Vertical and adiabatic values, benzenoid and nonbenzenoid aromatic hydrocarbons, and conjugated molecules with heteroatoms

Electron affinity of adsorbed dye monolayers

Chemical Sensitization, Spectral Sensitization, and Latent Image Formation in Silver Halide Photography

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