ChemInform Abstract: FORCE FIELD, DIPOLE MOMENT DERIVATIVES, AND VIBRONIC CONSTANTS OF BENZENE FROM A COMBINATION OF EXPERIMENTAL AND AB INITIO QUANTUM CHEMICAL INFORMATION

Pulay, P.; Fogarasi, Géza; Boggs, James E.

doi:10.1002/chin.198129079

Cited by 6 publications

(8 citation statements)

References 1 publication

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“…The equilibrium geometry of the benzene molecule was obtained at the B3LYP 24 /cc-pVDZ 25 level using the Gaussian package, 26 giving very good agreement with the experimental values for the geometry and vibrational frequencies. 27,28 The resulting ionization spectrum is shown in Figure 1a. Each line in the spectrum represents an ionic eigenstate and is located at the corresponding ionization energy.…”

mentioning

confidence: 99%

Attosecond Hole Migration in Benzene Molecules Surviving Nuclear Motion

Despré

Marciniak

Loriot

et al. 2015

J. Phys. Chem. Lett.

120

118

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Hole migration is a fascinating process driven by electron correlation, in which purely electronic dynamics occur on a very short time scale in complex ionized molecules, prior to the onset of nuclear motion. However, it is expected that due to coupling to the nuclear dynamics, these oscillations will be rapidly damped and smeared out, which makes experimental observation of the hole migration process rather difficult. In this Letter, we demonstrate that the instantaneous ionization of benzene molecules initiates an ultrafast hole migration characterized by a periodic breathing of the hole density between the carbon ring and surrounding hydrogen atoms on a subfemtosecond time scale. We show that these oscillations survive the dephasing introduced by the nuclear motion for a long enough time to allow their observation. We argue that this offers an ideal benchmark for studying the influence of hole migration on molecular reactivity.

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confidence: 99%

Attosecond Hole Migration in Benzene Molecules Surviving Nuclear Motion

Despré

Marciniak

Loriot

et al. 2015

J. Phys. Chem. Lett.

120

118

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“…The cubic force constant is taken as in Ref. (25); the frequencies for the C-H and C-D bond stretch can be found in Ref. (26).…”

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confidence: 99%

A New Method for the Determination of the Dynamic Isotope Effect and the Deuterium Quadrupole Coupling Constant in Liquids

Hardy

Witt

Dölle

et al. 1998

Journal of Magnetic Resonance

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“…For exoergic processes, the displacement d between the minima of the oscillators must be replaced by the barrier width ∆ x , which is the horizontal distance between the turning points of vibration of the oscillator in the initial and final states of a radiationless transition, where the harmonic force constant of the vibrational mode is given by its angular frequency of oscillation, , knowing the oscillator reduced mass µ . For example, the asymmetric CC stretching mode of benzene is observed at 1309 cm –1 and can be reproduced with a harmonic force field using a CC stretching mode with a force constant f CC ≈ 1000 kcal mol –1 Å –2 60 . This vibration of the benzene ring is also described as the Kekulé mode and corresponds to three CC oscillators being simultaneously displaced from their equilibrium positions in the transfer of benzene from the initial to the final state.…”

Section: Methodsmentioning

confidence: 99%

Higher activation barriers can lift exothermic rate restrictions in electron transfer and enable faster reactions

et al. 2018

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Electron transfer reactions are arguably the simplest chemical reactions but they have not yet ceased to intrigue chemists. Charge-separation and charge-recombination reactions are at the core of life-sustaining processes, molecular electronics and solar cells. Intramolecular electron donor-acceptor systems capture the essential features of these reactions and enable their fundamental understanding. Here, we report intramolecular electron transfers covering a range of 100 kcal mol−1 in exothermicities that show an increase, then a decrease, and finally an increase in rates with the driving force of the reactions. Concomitantly, apparent activation energies change from positive, to negative and finally to positive. Reactions with positive activation energies are found to be faster than analogous reactions with negative effective activation energies. The increase of the reorganization energy with the driving force of the reactions can explain the peculiar free-energy relationship observed in this work.

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ChemInform Abstract: FORCE FIELD, DIPOLE MOMENT DERIVATIVES, AND VIBRONIC CONSTANTS OF BENZENE FROM A COMBINATION OF EXPERIMENTAL AND AB INITIO QUANTUM CHEMICAL INFORMATION

Cited by 6 publications

References 1 publication

Attosecond Hole Migration in Benzene Molecules Surviving Nuclear Motion

Attosecond Hole Migration in Benzene Molecules Surviving Nuclear Motion

A New Method for the Determination of the Dynamic Isotope Effect and the Deuterium Quadrupole Coupling Constant in Liquids

Higher activation barriers can lift exothermic rate restrictions in electron transfer and enable faster reactions

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