Long‐Range Charge Separation in Solvent‐Free Donor–Bridge–Acceptor Systems

Wegewijs, B.; Verhoeven, J. W.

doi:10.1002/9780470141656.ch5

Cited by 21 publications

(12 citation statements)

References 117 publications

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“…This aspect has been extensively studied in jet-cooled bichromophoric species. [37][38][39] THIQM is an interesting system in this respect as both internal solvation (hydrogen bond) and geometric constraints (equatorial or axial position of the lone pair) are expected to play a role.…”

Section: Discussionmentioning

confidence: 99%

Chirality-dependent hydrogen bond direction in jet-cooled (S)-1,2,3,4-tetrahydro-3-isoquinoline methanol (THIQM): IR-ion dip vibrational spectroscopy of the neutral and the ion

Mahjoub

Chakraborty

Lepère

et al. 2009

Phys. Chem. Chem. Phys.

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The structural modifications of (S)-1,2,3,4-tetrahydro-3-isoquinoline methanol (THIQM) upon ionisation have been investigated in jet-cooled conditions, by means of laser-induced fluorescence, REMPI, and IR-UV ion-dip spectroscopy of the neutral ground state and the ion. These results combined with ab initio calculations, support the presence in the jet of two low-energy conformers of THIQM. In the most stable Conformer I, the CH(2)OH substituent acts as a hydrogen bond donor to the nitrogen lone pair in the equatorial position. In this case, the nitrogen atom is in (S) configuration. Conformer II shows the opposite NHO hydrogen bond from the hydrogen atom in the equatorial position of nitrogen to the OH group. In this case, the nitrogen atom is in (R) configuration. This chirality dependence of the hydrogen bond direction is lost upon ionisation. While ionisation of Conformer II reinforces the NHO hydrogen bond, ionisation of Conformer I induces its isomerisation to the same ion as Conformer II, i.e. a change in hydrogen bond direction.

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Section: Discussionmentioning

confidence: 99%

Chirality-dependent hydrogen bond direction in jet-cooled (S)-1,2,3,4-tetrahydro-3-isoquinoline methanol (THIQM): IR-ion dip vibrational spectroscopy of the neutral and the ion

Mahjoub

Chakraborty

Lepère

et al. 2009

Phys. Chem. Chem. Phys.

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“…A convenient model system often used to probe intramolecular ET reactions by different experimental techniques comprises of a donor (D) and an acceptor (A) of electrons connected by molecular bridge (B) (for details see e.g. Jordan and Paddon-Row, 1992;Wasielewski, 1992;Miller et al, 1984a, b;Pullen et al, 1999;Warman et al, 1999;Wegewijs and Verhoeven, 1999;Sikes et al, 2001;Walters et al, 2003;Hviid et al, 2004;Weiss et al, 2004). The number and variety of such donor-bridge-acceptor (DBA) systems have grown explosively in recent years.…”

Section: Introductionmentioning

confidence: 99%

Intra-molecular electron transfer and electric conductance via sequential hopping: Unified theoretical description

Berlin

Ratner

2005

Radiation Physics and Chemistry

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“…The hypothesis that intramolecular modes can drive ET by themselves has also been advanced in the last decade (17), on the basis of several investigations of photoinduced charge separation in covalently linked D-br-A systems in solution (D ¼ donor, A ¼ acceptor, br ¼ bridge) (18), and was later confirmed by studies in supersonic jets under rigorous solvent-free conditions (17).…”

Section: Introductionmentioning

confidence: 99%

Role of Intramolecular Vibrations in Long-Range Electron Transfer between Pheophytin and Ubiquinone in Bacterial Photosynthetic Reaction Centers

Borrelli¹,

Donato

Peluso

2005

Biophysical Journal

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The dynamics of the elementary electron transfer step between pheophytin and primary ubiquinone in bacterial photosynthetic reaction centers is investigated by using a discrete state approach, including only the intramolecular normal modes of vibration of the two redox partners. The whole set of normal coordinates of the acceptor and donor groups have been employed in the computations of the Hamiltonian matrix, to reliably account both for shifts and mixing of the normal coordinates, and for changes in vibrational frequencies upon ET. It is shown that intramolecular modes provide not only a discrete set of states more strongly coupled to the initial state but also a quasicontinuum of weakly coupled states, which account for the spreading of the wave packet after ET. The computed transition probabilities are sufficiently high for asserting that electron transfer from bacteriopheophytin to the primary quinone can occur via tunneling solely promoted by intramolecular modes; the transition times, computed for different values of the electronic energy difference and coupling term, are of the same order of magnitude (10(2) ps) of the observed one.

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Long‐Range Charge Separation in Solvent‐Free Donor–Bridge–Acceptor Systems

Cited by 21 publications

References 117 publications

Chirality-dependent hydrogen bond direction in jet-cooled (S)-1,2,3,4-tetrahydro-3-isoquinoline methanol (THIQM): IR-ion dip vibrational spectroscopy of the neutral and the ion

Chirality-dependent hydrogen bond direction in jet-cooled (S)-1,2,3,4-tetrahydro-3-isoquinoline methanol (THIQM): IR-ion dip vibrational spectroscopy of the neutral and the ion

Intra-molecular electron transfer and electric conductance via sequential hopping: Unified theoretical description

Role of Intramolecular Vibrations in Long-Range Electron Transfer between Pheophytin and Ubiquinone in Bacterial Photosynthetic Reaction Centers

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