Electron affinities of some polycyclic aromatic hydrocarbons, obtained from electron-transfer equilibria

Crocker, Louis S.; Wang, Tiebang; Kebarle, P.

doi:10.1021/ja00070a030

Cited by 115 publications

(99 citation statements)

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“…(i) the orbital energies r and a are taken from experimental values of ionization potential and electron affinities whose have been reported from available literature; 50,51 (ii) intra-monomer coulomb integrals ( r i a i , r i r i , a i a i ) represent Coulombic repulsion between two electrons which is expressed by the following bi-electronic integral (i.e. for r i a i ) :…”

Section: Parameterization Of the Model For Dimer And Trimermentioning

confidence: 99%

Singlet fission in linear chains of molecules

Ambrosio

Troisi

2014

The Journal of Chemical Physics

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We develop a model configuration interaction Hamiltonian to study the electronic structure of a chain of molecules undergoing singlet fission. We first consider models for dimer and trimers and then we use a matrix partitioning technique to build models of arbitrary size able to describe the relevant electronic structure for singlet fission in linear aggregates. We find that the multi-excitonic state (ME) is stabilized at short inter-monomer distance and the extent of this stabilization depends upon the size of orbital coupling between neighboring monomers. We also find that the coupling between ME states located on different molecules is extremely small leading to bandwidths in the order of ~10meV. This observation suggests that multi-exciton states are extremely localized by electron-phonon coupling and that singlet fission involves the transition between a relatively delocalized Frenkel exciton and a strongly localized multi-exciton state. We adopt the methodology commonly used to study non-radiative transitions to describe the singlet fission dynamics in these aggregates and we discuss the limit of validity of the approach. The results indicate that the phenomenology of singlet fission in molecular crystals is different in many important ways from what is observed in isolated dimers.

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Section: Parameterization Of the Model For Dimer And Trimermentioning

confidence: 99%

Singlet fission in linear chains of molecules

Ambrosio

Troisi

2014

The Journal of Chemical Physics

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“…The peak positions correspond to the NIR and PIR states of the adsorbed molecule. These states are related to the ionization energy of 6.61 eV [21,22] and the electron affinity of 1.35 eV [23] of the free molecule. These energies are, however, shifted towards the Fermi level because of the electronic polarization of the NaCl film and the underlying metal [24].…”

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confidence: 99%

Molecules on Insulating Films: Scanning-Tunneling Microscopy Imaging of Individual Molecular Orbitals

et al. 2005

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Ultrathin insulating NaCl films have been employed to decouple individual pentacene molecules electronically from the metallic substrate. This allows the inherent electronic structure of the free molecule to be preserved and studied by means of low-temperature scanning-tunneling microscopy. Thereby direct images of the unperturbed molecular orbitals of the individual pentacene molecules are obtained. Elastic scattering quantum chemistry calculations substantiate the experimental findings.

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“…Charged species of the naphthalene molecule participate in many important electron-transfer chemical reactions in gas phase [1,2]. Naphthalene cations are the smallest polycyclic aromatic hydrocarbons involved in interstellar chemistry that have been detected by spectroscopic observations [3].…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…The reason for studying such properties of ionized molecules stems from the direct observation of charge-transfer states in aromatic hydrocarbons [1]. The energies of these states are often calculated assuming that ionic and neutral molecular polarizabilities are the same [1,9]. Low accuracy ab initio studies using the finite-field SCF method have shown that the polarizabilities of the neutral and charged species can be very different [10].…”

Section: Introductionmentioning

confidence: 99%

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Ab initio study of the static dipole polarizability of neutral and charged naphthalene

Machado

Hinchliffe

1997

Elect J Theoret Chem

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SUMMARYWe present an ab initio SCF-MO study of the static dipole polarizability of some neutral and charged species of naphthalene (C10H8) q , (q = −2, −1, 0, +1, +2). The charged species involve additions and removals of electrons to and from the HOMO and LUMO π-electron orbitals. The polarizability calculations were performed using the Coupled Perturbed Hartree-Fock method, and in addition, we used direct analytical differentiation of the energy expression. We used a series of split valence basis sets augmented with sp diffuse and polarized functions STO/6-31+G(md,np, (m = n = 1, 2, 3), and all geometries were fully optimized. Molecular structure optimizations were generally started from the geometry predicted for neutral naphthalene with D2h symmetry at the HF/6-31G** level of theory.The Hartree-Fock results indicate that the anisotropies of the components of the dipole polarizability tensor of neutral naphthalene (q = 0) are in agreement with our own previous theoretical calculations and with the experimental values corresponding to laser Stark spectroscopy in a naphthalene molecular beam. This agreement with experimental results can be further improved with extension of the number of polarized functions in the basis set.We also analyse the effect of the negative and positive charges on the naphthalene molecule on the polarizability tensor components. The variation of molecular geometry also plays a part in these changes.

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Electron affinities of some polycyclic aromatic hydrocarbons, obtained from electron-transfer equilibria

Cited by 115 publications

References 0 publications

Singlet fission in linear chains of molecules

Singlet fission in linear chains of molecules

Molecules on Insulating Films: Scanning-Tunneling Microscopy Imaging of Individual Molecular Orbitals

Ab initio study of the static dipole polarizability of neutral and charged naphthalene

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