Resonant tunneling through the repulsive Coulomb barrier of a quadruply charged molecular anion

Dau, Phuong Diem; Liu, Hongtao; Yang, Jiping; Winghart, Marc‐Oliver; Wolf, Thomas; Unterreiner, Andreas‐Neil; Weis, Patrick; Miao, Yurun; Ning, Chuangang; Kappes, Manfred M.; Wang, Lai-Sheng

doi:10.1103/physreva.85.064503

Cited by 29 publications

(26 citation statements)

References 23 publications

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“…4 More recently, it was also confirmed to be an important relaxation channel for the first singlet excited state (S 1 ) of the isolated bisdisulizole tetraanion ([BDSZ] 4− )-a strong fluorophore in solution. 11 [BDSZ] 4− , like the metal phthalocyanine based tetraanions is electronically metastable. However, excited state electron tunneling detachment (ESETD) can also occur for electronically stable multianions as recently shown both by the Verlet group 12,13 and by several of us.…”

Section: Introductionmentioning

confidence: 99%

Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

Winghart

Yang

Vonderach

et al. 2016

The Journal of Chemical Physics

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Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt2(μ-P2O5H2)4 + 2H](2-) after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet (1)A2u state and concomitant rise in population of the triplet (3)A2u state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet (1)A2u state takes only a few picoseconds, ESETD from the triplet (3)A2u state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt2(μ-P2O5H2)4 + 2H](2-) is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

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Section: Introductionmentioning

confidence: 99%

Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

Winghart

Yang

Vonderach

et al. 2016

The Journal of Chemical Physics

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“…10,[26][27][28][30][31][32][33][34] We have designed a PE imaging system, which replaced the magnetic-bottle electron analyzer on our first generation ESI-PES apparatus at room temperature, 35 and studied the angular distributions of photoelectrons from multiply charged anions. [36][37][38][39] We have recently developed a highresolution PE imaging system, which can achieve electron kinetic energy resolutions down to 1.4 cm −1 for low energy electrons. 40,41 We have also built an improved version of our cryogenically controlled ion trap coupled with our ESI source in a more compact design, in which the 90 o ion bender is eliminated.…”

Section: Introductionmentioning

confidence: 99%

High-resolution photoelectron imaging of cold ${\rm C}_{60}^ -$C60− anions and accurate determination of the electron affinity of C60

Huang

Dau

Liu

et al. 2014

The Journal of Chemical Physics

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High-resolution photoelectron imaging and spectroscopy of cold C₆₀⁻ anions are reported using a newly built photoelectron imaging apparatus coupled with an electrospray ionization source and a temperature-controlled cryogenic ion trap. Vibrationally resolved photoelectron spectra are obtained for the detachment transition from the ground state of C₆₀⁻ to that of C60 at various detachment wavelengths from 354.84 nm to 461.35 nm. The electron affinity of C60 is accurately measured to be 2.6835 ± 0.0006 eV. Numerous unexpected vibrational excitations are observed in the photoelectron spectra due to the Jahn-Teller effect in C₆₀⁻ and Hertzberg-Teller vibronic coupling in both C₆₀⁻ and C60. Both the relative intensities of vibrational peaks and their photoelectron angular distributions provide evidence for the vibronic couplings. The observed p-wave-like behavior in the angular distribution of the 0₀⁰ transition suggests that the electron is detached from an s-type orbital.

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“…22,24 The latter has been conveniently enabled by photoelectron (PE) spectroscopy of the polyanion. 19,22,[25][26][27] Consider a dianion, as in the case of [ATP-H2] 2-. In the absence of photo-excited states, the RCB height shown in Figure 1(a) can be directly measured from an electron kinetic energy (eKE) cut-off in the PE spectra below which a PE cannot be emitted.…”

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confidence: 99%

“…Note that even if a resonance is above the RCB saddle point, it may still be subject to emission by tunneling as shown for the fluorescein dianion 28 and the bisdisulizole tetraanion. 27 Very recently, Daly et al have shown that electron circular dichroism can be observed for chiral DNA strands. 39 Here, we show that tunneling may be efficient in DNA fragments and that PE imaging may offer some insight into the emission process.…”

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confidence: 99%

Site-Specific Photo-oxidation of the Isolated Adenosine-5′-triphosphate Dianion Determined by Photoelectron Imaging

Castellani

Avagliano

González

et al. 2020

J. Phys. Chem. Lett.

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Photoelectron imaging of the isolated adenosine-5´-triphosphate dianion excited to the 1 ππ* states reveals that electron emission is predominantly parallel to the polarization axis of the light and arises from subpicosecond electron tunneling through the repulsive Coulomb barrier (RCB). The computed RCB shows that the most probable electron emission site is on the amino group of adenine. This is consistent with the photoelectron imaging: excitation to the 1 ππ* states leads to an aligned ensemble distributed predominantly parallel to the long axis of adenine, the subsequent electron tunneling site is along this axis, and the negatively charged phosphate groups guide the outgoing electron mostly along this axis at long range. Imaging electron tunneling from polyanions combined with computational chemistry may offer a general route to probing the intrinsic photo-oxidation site and dynamics as well as overall structure of complex isolated species.

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Resonant tunneling through the repulsive Coulomb barrier of a quadruply charged molecular anion

Cited by 29 publications

References 23 publications

Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

High-resolution photoelectron imaging of cold ${\rm C}_{60}^ -$C60− anions and accurate determination of the electron affinity of C60

Site-Specific Photo-oxidation of the Isolated Adenosine-5′-triphosphate Dianion Determined by Photoelectron Imaging

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