Structures and Binding Energies of the Naphthalene Dimer in Its Ground and Excited States

Dubinets, Nikita O.; Сафонов, А. А.; Bagatur’yants, A. A.

doi:10.1021/acs.jpca.6b03761

Cited by 34 publications

(45 citation statements)

References 25 publications

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“…The naphthalene dimer is a rather typical and well‐studied system. The reported binding energies for the naphthalene dimer in the ground state are in the range from –4.6 kcal/mol to –6.2 kcal/mol, depending on the pair geometry . Our values are 3–4 times higher, because of the much larger systems, 141 atoms instead of 36 in the naphthalene dimer, and, correspondingly, the number of contacting atoms in pairs 1–4, so that we can expect a much stronger dispersion interaction in our case.…”

Section: Resultssupporting

confidence: 89%

MD/QC Simulation of the Structure and Spectroscopic Properties of α-NPD-BAlq Exciplexes at an α-NPD/BAlq Interface in OLEDs

2017

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The structure and spectroscopic properties of exciplexes formed at an interface between a hole‐transporting layer of N,N′‐di(naphthalen‐2‐yl)‐N,N′‐diphenyl‐benzidine (α‐NPD) and an electron transporting layer of bis(2‐methyl‐8‐quinolinato)(4‐phenylphenolato)‐aluminum (BAlq) in an OLED are investigated by multiscale (molecular dynamics, MD, and quantum chemistry, QC) simulations. Four α‐NPD–BAlq pairs with different orientations of components are selected from the central 5‐nm slab with the interface for subsequent QC calculations. Calculations for these pairs are performed within DFT/PBE0 and DFT/BHandHLYP approaches for the ground state and TDDFT/PBE0 and TDDFT/BHandHLYP approaches for the excited state with inclusion of D3BJ dispersion corrections. The calculated binding energies of the complexes are in the range from –19.0 to –24.7 kcal/mol in the ground state and from –21.9 to –34.1 kcal/mol in the excited state. The calculated S1 excited states are characterized by strong intermolecular charge transfer, and the corresponding S1→S0 transition energies are in good agreement with the available experimental data.

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Section: Resultssupporting

confidence: 89%

MD/QC Simulation of the Structure and Spectroscopic Properties of α-NPD-BAlq Exciplexes at an α-NPD/BAlq Interface in OLEDs

2017

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“…Recent ab initio studies of naphthalene dimers are consistent with this picture, showing a small preference (around 1-2 kcal mol À1 ) for parallel-displaced arrangements over perpendicular ones. 17,23,46 Interestingly, Grimme 17 shows that for aromatics larger than benzene, the increased stability of parallel stacking is due to the orbital dependent part of the dispersion energy, rather than the classical r À6 component.…”

Section: 17mentioning

confidence: 99%

The structures of liquid pyridine and naphthalene: the effects of heteroatoms and core size on aromatic interactions

Headen

Cullen

Patel

et al. 2018

Phys. Chem. Chem. Phys.

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Total neutron scattering has been used in conjunction with H/D and *N/ 15 N isotopic substitution to determine the detailed liquid-state structures of pyridine and naphthalene. Analysis of the data via an empirical potential-based structure refinement method has allowed us to interrogate the full six-dimensional spatial and orientational correlation surfaces in these systems, and thereby to deduce the fundamental effects of a heteroatom and aromatic core-size on intermolecular p-p interactions. We find that the presence of a nitrogen heteroatom, and concomitant dipole moment, in pyridine induces surprisingly subtle departures from the structural correlations observed in liquid benzene: in both cases the most probable local motif is based on perpendicular (edge-to-face) intermolecular contacts, while parallel-displaced configurations give rise to a clear shoulder in the correlation surface. However, the effect of the heteroatom is revealed through detailed analysis of the intermolecular orientational correlations. This analysis shows a tendency for neighbouring pyridine molecules to direct one meta-and one para-hydrogen towards the neighbouring aromatic p-orbitals in edge-to-face configurations, while head-to-tail alignment of adjacent nitrogen atoms is favoured in faceto-face configurations. In contrast to this, increasing aromatic core size from one to only two rings has a clear and profound effect on the p-p interactions and liquid structure. Our experiments show that naphthalenenaphthalene contacts are dominated by parallel-displaced configurations, akin to those found in graphite. This marks a fundamental difference with the structure of liquid benzene, in which perpendicular geometries are favoured. Furthermore, it is remarkable to note that in the systems studied, the most favoured spatioorientational configurations observed in the liquid state are not predicted from ab initio calculations and/or solid state crystallographic studies. This highlights the need for caution when extrapolating the results of crystallographic and computational studies to aromatic interactions in liquids and disordered systems.

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“…It should be noted that for processes involving chiral systems the dependence on concentration is typical and is usually explained by the tendency of chiral compounds to form associates . It is known that naphthalene and its substituted derivatives, as well as NPX, form dimers and excimers in the solid state and in solution . In particular, the NPX–NPX dyad excimer is described herein .…”

Section: Introductionmentioning

confidence: 98%

Spin Selectivity in Chiral Linked Systems

Ageeva

Khramtsova

Magin

et al. 2018

Chemistry A European J

105

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This work has shown spin selectivity in electron transfer (ET) of diastereomers of (R,S)-naproxen-(S)-N-methylpyrrolidine and (R,S)-naproxen-(S)-tryptophan dyads. Photoinduced ET in these dyads is interesting because of the still unexplained phenomenon of stereoselectivity in the drug activity of enantiomers. The chemically induced dynamic nuclear polarization (CIDNP) enhancement coefficients of (R,S)-diastereomers are double those of the (S,S)-analogue. These facts are also interesting because spin effects are among the most sensitive, even to small changes in spin and molecular dynamics of paramagnetic particles. Therefore, CIDNP reflects the difference in magnetoresonance parameters (hyperfine interaction constants (HFIs), g-factor difference) and lifetimes of the paramagnetic forms of (R,S)- and (S,S)-diastereomers. The difference in HFI values for diastereomers has been confirmed by a comparison of CIDNP experimental enhancement coefficients with those calculated. Additionally, the dependence of the CIDNP enhancement coefficients on diastereomer concentration has been observed for the naproxen-N-methylpyrrolidine dyad. This has been explained by the participation of ET in homo-(R,S-R,S or S,S-S,S) and hetero-(R,S-S,S) dimers of dyads. In this case, the effectivity of ET, and consequently, CIDNP, is supposed to be different for (R,S)- and (S,S)-homodimers, heterodimers, and monomers. The possibility of dyad dimer formation has been demonstrated by using high-resolution X-ray and NMR spectroscopy techniques.

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Structures and Binding Energies of the Naphthalene Dimer in Its Ground and Excited States

Cited by 34 publications

References 25 publications

MD/QC Simulation of the Structure and Spectroscopic Properties of α-NPD-BAlq Exciplexes at an α-NPD/BAlq Interface in OLEDs

MD/QC Simulation of the Structure and Spectroscopic Properties of α-NPD-BAlq Exciplexes at an α-NPD/BAlq Interface in OLEDs

The structures of liquid pyridine and naphthalene: the effects of heteroatoms and core size on aromatic interactions

Spin Selectivity in Chiral Linked Systems

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