Electronic and ionic properties of molecular TTF and TCNQ

Klots, Cornelius E.; Compton, R. N.; Raaen, Vernon F.

doi:10.1063/1.1681130

Cited by 99 publications

(44 citation statements)

References 12 publications

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“…This provides a detachment energy of 2.9 eV, which is in good agreement with the measured electron affinity of 2.8 ± 20 0.1 eV. 14 The broader kinetic energy feature around 2.0 eV is somewhat unexpected. The photon energy of 3.1 eV is resonant with the D 2 state and as such, this photoelectron peak could be explained in terms of resonance-enhanced two- 25 photon absorption via the D 2 state, which has a large excitation cross-section.…”

Section: Resultssupporting

confidence: 82%

Spectroscopy and dynamics of the 7,7,8,8-tetracyanoquinodimethane radical anion

Roberts

Lecointre

Horke

et al. 2010

Phys. Chem. Chem. Phys.

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Publisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. The photoelectron spectrum of the 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical anion has been measured at 3.1 eV. Additionally, the ultrafast relaxation dynamics of the first excited state (1 2 B 3u ) of TCNQ -have been studied using time-resolved photoelectron spectroscopy, which reveals that it undergoes internal conversion back to the ground state ( 2 B 2g ) with an associated 10 lifetime of 650 fs and shows evidence of coherent nuclear motion.

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Section: Resultssupporting

confidence: 82%

Spectroscopy and dynamics of the 7,7,8,8-tetracyanoquinodimethane radical anion

Roberts

Lecointre

Horke

et al. 2010

Phys. Chem. Chem. Phys.

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“…As shown in Table 2, the frequencies of the stiff modes usually decrease upon electron attachment. In particular, this tendency manifests itself especially for b 1u , b 2u , b 3g , and a g symmetry modes and the largest shifts we observe for ν 31 . We consider these as core-excited states because they were formed by promoting an electron in the ground 1 2 B 1g state from a doubly occupied orbital (either 3b 1g or 4b 3u ) to the 4b 2g orbital (which is the LUMO in the neutral).…”

Section: Neutral Tcnq-f4 and The Lowest (Ground) Doubletmentioning

confidence: 76%

Bound-Excited Electronic States of the Anion of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane

2003

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The doublet anionic states of 3,5,7,8, have been studied at the Hartree-Fock and the Møller-Plesset (MP) perturbation theory levels (up to fourth order) with aug(sp)-pVDZ basis sets. Our results indicate that TCNQ-F4 forms a stable anion of B 2g symmetry whose vertical electron attachment energy is 2.893 eV (at the MP4 level). In addition, we found two valence excited electronic states (2 2 B 3u and 1 2 A g ) of the anion that are stable vertically with respect to the neutral parent. The electronic stability of the third excited state (a core-excited 1 2 B 3u state) needs to be further investigated. We conclude that the neutral TCNQ-F4 at its equilibrium D 2h geometry may attach an excess electron to form any of these four states (i.e., 1 2 B 2g , 1 2 B 3u , 2 2 B 3u , and 1 2 A g ) and the corresponding MP4 vertical attachment energies (VAE) are 2.893, 0.822, 0.244, and 0.072 eV, respectively. However, due to second-order Jahn-Teller distortion, only the ground anionic state (1 2 B 2g ) possesses a minimum at D 2h symmetry. For the two valence excited states (2 2 B 3u and 1 2 A g ), negative curvatures cause out-of-plane deformations that lead to (i) an increase of the energy of the latter (1 2 A g ) state and (ii) achieving a minimumenergy structure of C 2 symmetry for the former where this state becomes a doublet A state and its vertical electronic stability increases to 2.721 eV.

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“…21 Even in the ground state, the extra electron is usually bound too weakly to the neutral molecule to support bound excited states. There are, however, some well-known examples (e.g., tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) [22][23][24][25][26] ) that are able to bind an excess electron and form a few bound excited anionic states.…”

Section: Resultsmentioning

confidence: 99%

An Unstable Anion Stabilized in a Molecular Trap

Skurski

Simons

2000

J. Phys. Chem. A

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The possibility of stabilizing an electronically metastable anion in a molecular trap is studied using ab initio electronic structure methods. The 2 Π g N 2 -d-wave shape resonance state is used as a prototype for the metastable anion solute, and a pair of inwardly oriented LiCN molecules (NCLi‚‚‚LiCN) is used as a prototypical trap. It is found that for the (NCLi‚‚‚LiCN) trap at its local minimum geometry, the 2 Π g state becomes electronically stable and is the ground state of the system. It is also found that, in this model trap, two other (excited) anionic states are bound ( 2 Σ g and 2 Π u ) one of which is a trap-bound state and the second of which is another stabilized resonance state. Moreover, calculations performed on traps of varying strength (which we alter by varying the trap size) show that the number of bound anionic states strongly depends on the trap's strength. Detailed numerical results are presented for the (NCLi‚‚‚NtN‚‚‚LiCN)-trap plus solute anion whose vertical electron detachment energy is 3.250 eV, but the results obtained are suggestive of a wide variety of such trap-stabilized anion systems.

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Electronic and ionic properties of molecular TTF and TCNQ

Cited by 99 publications

References 12 publications

Spectroscopy and dynamics of the 7,7,8,8-tetracyanoquinodimethane radical anion

Spectroscopy and dynamics of the 7,7,8,8-tetracyanoquinodimethane radical anion

Bound-Excited Electronic States of the Anion of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane

An Unstable Anion Stabilized in a Molecular Trap

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