Van der Waals Complexes of Polar Aromatic Molecules:  Unexpected Structures for Dimers of Azulene

Piacenza, Manuel; Grimme, Stefan

doi:10.1021/ja053613q

Cited by 94 publications

(75 citation statements)

References 52 publications

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“…The most widely applied and very well tested method is DFT-D 9 (with BLYP 18,19 and PBE 20 functionals), which proved high accuracy in many different applications. [21][22][23][24] After two years of careful testing and validation, however, knowledge of a few shortcomings of the original DFT-D method accumulated, which will be also addressed in the present work:…”

Section: Introductionmentioning

confidence: 99%

Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction

2006

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A new density functional (DF) of the generalized gradient approximation (GGA) type for general chemistry applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C(6) x R(-6). A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common density functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on standard thermochemical benchmark sets, for 40 noncovalently bound complexes, including large stacked aromatic molecules and group II element clusters, and for the computation of molecular geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for standard functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean absolute deviation of only 3.8 kcal mol(-1). The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the average CCSD(T) accuracy. The basic strategy in the development to restrict the density functional description to shorter electron correlation lengths scales and to describe situations with medium to large interatomic distances by damped C(6) x R(-6) terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chemical method for large systems where dispersion forces are of general importance.

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Section: Introductionmentioning

confidence: 99%

Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction

2006

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“…49 They found that the most stable structure for the azulene neutral dimer is not an antiparallel -stacked geometry but an unexpected -stacked geometry where the two seven-membered rings are located almost on top of each other and the long molecular axes are rotated against each other by 130°. 49 They found that the most stable structure for the azulene neutral dimer is not an antiparallel -stacked geometry but an unexpected -stacked geometry where the two seven-membered rings are located almost on top of each other and the long molecular axes are rotated against each other by 130°.…”

Section: F Conditions For the Formation Of Isomer Ii-1/ii-2mentioning

confidence: 99%

Photoelectron spectroscopy of cluster anions of naphthalene and related aromatic hydrocarbons

Ando

Mitsui

Nakajima

2008

The Journal of Chemical Physics

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The electronic structures and structural morphologies of naphthalene cluster anions, (naphthalene)(n)(-) (n=3-150), and its related aromatic cluster anions, (acenaphthene)(n)(-) (n=4-100) and (azulene)(n)(-) (n=1-100), are studied using anion photoelectron spectroscopy. For (naphthalene)(n) (-) clusters, two isomers coexist over a wide size range: isomers I and II-1 (28 < or = n < or =60) or isomers I and II-2 (n > or = ~60). Their contributions to the photoelectron spectra can be separated using an anion beam hole-burning technique. In contrast, such an isomer coexistence is not observed for (acenaphthene)(n) (-) and (azulene)(n) (-) clusters, where isomer I is exclusively formed throughout the whole size range. The vertical detachment energies (VDEs) of isomer I (7 < or = n < or = 100) in all the anionic clusters depend linearly on n(-13) and their size-dependent energetics are quite similar to one another. On the other hand, the VDEs of isomers II-1 and II-2 produced in (naphthalene)(n)(-) clusters with n > or = approximately 30 remain constant at 0.84 and 0.99 eV, respectively, 0.4-0.6 eV lower than those of isomer I. Based upon the ion source condition dependence and the hole-burning photoelectron spectra experiments for each isomer, the energetics and characteristics of isomers I, II-1, and II-2 are discussed: isomer I is an internalized anion state accompanied by a large change in its cluster geometry after electron attachment, while isomers II-1 and II-2 are crystal-like states with little structural relaxation. The nonappearance of isomers II-1 and II-2 for (acenaphthene)(n)(-) and (azulene)(n)(-) and a comparison with other aromatic cluster anions indicate that a highly anisotropic and symmetric pi-conjugated molecular framework, such as found in the linear oligoacenes, is an essential factor for the formation of the crystal-like ordered forms (isomers II-1 and II-2). On the other hand, lowering the molecular symmetry makes their production unfavorable.

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“…47 Further examples for accurate results on related molecules can be found in Refs. [48][49][50]. Recently, Rahman and colleagues 51 have investigated nucleobases on graphene using several variants of vdW corrections.…”

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confidence: 99%

Non-covalent functionalization of single wall carbon nanotubes and graphene by a conjugated polymer

Jiwuer

Abdurahman

Gülseren

et al. 2014

Applied Physics Letters

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We report first-principles calculations on the binding of poly[(9,9-bis-(6-bromohexylfluorene-2,7-diyl)-co-(benzene-1,4-diyl)] to a (8,0) single wall carbon nanotube (SWCNT) and to graphene. Considering different relative orientations of the subsystems, we find for the generalized gradient approximation a non-binding state, whereas the local density approximation predicts reasonable binding energies. The results coincide after inclusion of van der Waals corrections, which demonstrates a weak interaction between the polymer and SWCNT/graphene, mostly of van der Waals type. Accordingly, the density of states shows essentially no hybridization. The physisorption mechanism explains recent experimental observations and suggests that the conjugated polymer can be used for non-covalent functionalization. © 2014 AIP Publishing LLC

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Van der Waals Complexes of Polar Aromatic Molecules: Unexpected Structures for Dimers of Azulene

Cited by 94 publications

References 52 publications

Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction

Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction

Photoelectron spectroscopy of cluster anions of naphthalene and related aromatic hydrocarbons

Non-covalent functionalization of single wall carbon nanotubes and graphene by a conjugated polymer

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