Direct ab initio molecular dynamics (MD) study of the ionization on a benzene dimer

Tachikawa, Hiroto

doi:10.1039/c2ra20246h

Cited by 12 publications

(7 citation statements)

References 39 publications

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“…The center-of-mass separation was determined experimentally to be 4.96 Å. In ref , it was shown that (i) in the cationic dimer, 93% of the positive charge remains in the benzene whose hydrogen points to the center of the other benzene, similar (but not exactly equal) to Figure c, and (ii) the ionization energy of benzene is decreased with dimer formation by 100 meV, in our notation E P + = I g – I d = 100 meV. The first result further justifies our interest for studying charge entirely confined to a single molecule and is reproduced in our results since, of the two T-shaped dimers of Figures b and c, the one in Figure c has the lowest energy.…”

Section: Resultssupporting

confidence: 59%

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Extended Hückel Method Calculation of Polarization Energies: The Case of a Benzene Dimer

Tromer¹,

Freire²

2013

J. Phys. Chem. A

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We adapted Hoffmann's extended Hückel method to an interacting molecular system and use this approach to compute the electron affinity and ionization potential of benzene dimers. We restrict the added charge to one of the molecules and argue that the dimer energy computed in this manner is the relevant energy in any meaningful thermally activated hopping rate expression. The dimer electron affinity and ionization potential differs from the isolated molecule corresponding quantity by what is called polarization energy. The polarization energy normally stabilizes the anion and this is particularly relevant for benzene, given that its isolated anion is unstable with respect to charge detachment. We found that the anionic benzene dimer is only stabilized in certain conformations, suggesting that the stabilization of a benzene anion in an amorphous environment is very unlikely. The modest computational cost of the method makes it a viable alternative to compute the energy of charged molecules in amorphous molecular films, a central issue in the problem of charge transport in organic electronics.

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Section: Resultssupporting

confidence: 59%

“…The cation dimer results are more interesting since this dimer actually exists, it was first observed experimentally in the gas phase by Ohashi and Nishi . Recently the cation dimer morphology was elucidated by the ab initio calculations of Tachikawa . In this work the whole ionization process of a neutral dimer was investigated.…”

Section: Resultsmentioning

confidence: 87%

Extended Hückel Method Calculation of Polarization Energies: The Case of a Benzene Dimer

Tromer¹,

Freire²

2013

J. Phys. Chem. A

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“…All static ab initio calculations were carried out using the Gaussian 09 and GAMESS programs. [17,18] In the direct AIMD calculations [19][20][21][22][23][24][25] the potential energy and its gradient were calculated at the CAM-B3LYP/6-311 + +G(d,p) level for the reaction systems and used without basis set superposition error (BSSE) corrections in the trajectory calculation. The equation of motion was solved by the velocity Verlet algorithm with a time step of 0.25 fs.…”

Section: Methods Of Calculationmentioning

confidence: 99%

Mechanism of Dissolution of a Lithium Salt in an Electrolytic Solvent in a Lithium Ion Secondary Battery: A Direct Ab Initio Molecular Dynamics (AIMD) Study

Tachikawa

2014

ChemPhysChem

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The mechanism of dissolution of the Li+ ion in an electrolytic solvent is investigated by the direct ab initio molecular dynamics (AIMD) method. Lithium fluoroborate (Li+BF4−) and ethylene carbonate (EC) are examined as the origin of the Li+ ion and the solvent molecule, respectively. This salt is widely utilized as the electrolyte in the lithium ion secondary battery. The binding of EC to the Li+ moiety of the Li+BF4− salt is exothermic, and the binding energies at the CAM–B3LYP/6‐311++G(d,p) level for n=1, 2, 3, and 4, where n is the number of EC molecules binding to the Li+ ion, (EC)n(Li+BF4−), are calculated to be 91.5, 89.8, 87.2, and 84.0 kcal mol−1 (per EC molecule), respectively. The intermolecular distances between Li+ and the F atom of BF4− are elongated: 1.773 Å (n=0), 1.820 Å (n=1), 1.974 Å (n=2), 1.942 Å (n=3), and 4.156 Å (n=4). The atomic bond populations between Li+ and the F atom for n=0, 1, 2, 3, and 4 are 0.202, 0.186, 0.150, 0.038, and 0.0, respectively. These results indicate that the interaction of Li+ with BF4− becomes weaker as the number of EC molecules is increased. The direct AIMD calculation for n=4 shows that EC reacts spontaneously with (EC)3(Li+BF4−) and the Li+ ion is stripped from the salt. The following substitution reaction takes place: EC+(EC)3(Li+BF4−)→(EC)4Li+−(BF4−). The reaction mechanism is discussed on the basis of the theoretical results.

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“…Unlike the known benzene dimers with T-shaped (edgeto-face) and displaced-stacked (face-to-face) structures, where interaction between two benzene molecule is non-covalent (see, e.g. [4][5][6][7][8][9]), it is found that these molecules may also make a chemically bound state (we call this state a bi-benzene). We have also found that, in addition to a symmetric bi-benzene, three distorted allotropes of this compound molecule may exist.…”

Section: Introductionmentioning

confidence: 94%

Pseudo Jahn–Teller effect in stacked benzene molecules

2015

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Direct ab initio molecular dynamics (MD) study of the ionization on a benzene dimer

Cited by 12 publications

References 39 publications

Extended Hückel Method Calculation of Polarization Energies: The Case of a Benzene Dimer

Extended Hückel Method Calculation of Polarization Energies: The Case of a Benzene Dimer

Mechanism of Dissolution of a Lithium Salt in an Electrolytic Solvent in a Lithium Ion Secondary Battery: A Direct Ab Initio Molecular Dynamics (AIMD) Study

Pseudo Jahn–Teller effect in stacked benzene molecules

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