Binding energies in benzene dimers: Nonlocal density functional calculations

Puzder, Aaron; Dion, Maxime; Langreth, David C.

doi:10.1063/1.2189229

Cited by 158 publications

(185 citation statements)

References 45 publications

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“…It completely fails in describing van der Waals binding between (stacked) p-systems. Authors who tried to account for this deficiency, either by a first-principles approach, 40 or by fitting functionals to interaction energies, 51 or by DFT + dispersion (DFT-D) methods, 45,46,52 have often included the benzene dimer in their training and/or validation sets.…”

Section: Introductionmentioning

confidence: 99%

Vibration–rotation-tunneling states of the benzene dimer: an ab initio study

Avoird

Podeszwa

Szalewicz

et al. 2010

Phys. Chem. Chem. Phys.

152

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An improved intermolecular potential surface for the benzene dimer is constructed from interaction energies computed by symmetry-adapted perturbation theory, SAPT(DFT), with the inclusion of third-order contributions. Twelve characteristic points on the surface have been investigated also using the coupled-cluster method with single, double, and perturbative triple excitations, CCSD(T), and triple-zeta quality basis sets with midbond functions. The SAPT and CCSD(T) results are in close agreement and provide the best representation of these points to date. The potential was used in calculations of vibration-rotation-tunneling (VRT) levels of the dimer by a method appropriate for large amplitude intermolecular motions and tunneling between multiple equivalent minima in the potential. The resulting VRT levels were analyzed with the use of the permutation-inversion full cluster tunneling (FCT) group G 576 and a chain of subgroups that starts from the molecular symmetry group C s (M) of the rigid dimer at its equilibrium C s geometry and leads to G 576 if all possible intermolecular tunneling mechanisms are feasible. Further information was extracted from the calculated wave functions. It was found, in agreement with the experimental data, that for all of the 54 G 576 symmetry species (with different nuclear spin statistical weights) the lower VRT states have a tilted T-shape (TT) structure; states with the parallel-displaced structure are higher in energy than the ground state of A + 1 symmetry by at least 30 cm À1 . The dissociation energy D 0 equals 870 cm À1 , while the depth D e of the TT minimum in the potential is 975 cm À1 . Hindered rotation of the cap in the TT structure and tilt tunneling lead to level splittings on the order of 1 cm À1 . Also intermolecular vibrations with excitation energies starting at a few cm À1 were identified. A further small, but probably significant, level splitting was assigned to cap turnover, although in scans of the potential surface we could not find a plausible 'reaction path' for this process. Rotational constants were extracted from energy levels calculated for total angular momentum J = 0 and 1, and from expectation values of the inertia tensor. Although the end-over-end rotational constant B + C agrees well with the measured microwave spectra, there is disagreement with the measurements concerning the (a)symmetric rotor character of the benzene dimer. It is concluded from calculations for the 54 nuclear spin species that the microwave spectrum should show overlapping contributions from many different species. Another interesting conclusion regards the role of the quantum number K, for a prolate near-symmetric rotor the projection of the total angular momentum on the prolate axis. For the benzene dimer, K has a substantial effect on the energy levels associated with the intermolecular motions of the complex.

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Section: Introductionmentioning

confidence: 99%

Vibration–rotation-tunneling states of the benzene dimer: an ab initio study

Avoird

Podeszwa

Szalewicz

et al. 2010

Phys. Chem. Chem. Phys.

152

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“…1,[30][31][32][33][34][35][36][37][38][39] Both experimental 18,28,40 and theoretical [30][31][32][33][34][35] studies suggest that the benzene dimer has two almost isoenergetic geometries: T-shaped and paralleldisplaced. At the coupled cluster with singles, doubles, and perturbative triples [CCSD(T)] 41 level in an estimated complete basis set limit, the gas-phase binding energies D e (D o ) of these geometries were calculated to be 2.7 (2.4) and 2.8 (2.7) kcal/mol, respectively.…”

Section: Introductionmentioning

confidence: 99%

Modeling π–π Interactions with the Effective Fragment Potential Method: The Benzene Dimer and Substituents

2008

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This study compares the results of the general effective fragment potential (EFP2) method to the results of a previous combined coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] and symmetry-adapted perturbation theory (SAPT) study [Sinnokrot and Sherrill, J. Am. Chem. Soc., 2004, 126, 7690] on substituent effects in π-π interactions. EFP2 is found to accurately model the binding energies of the benzene-benzene, benzene-phenol, benzene-toluene, benzene-fluorobenzene, and benzene-benzonitrile dimers, as compared with high-level methods [Sinnokrot and Sherrill, J. Am. Chem. Soc., 2004, 126, 7690], but at a fraction of the computational cost of CCSD(T). In addition, an EFP-based Monte Carlo/simulated annealing study was undertaken to examine the potential energy surface of the substituted dimers.

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“…To capture these effects, a given vdW model has to correctly describe both the monomer screening and polarizability as well as the intermolecular coupling of these anisotropic fluctuations (see the short-range α sr (r,r′) and its long-range coupling in eq 22). This difficult task may be one of the underlying reasons why many secondorder vdW methods, which neglect such effects, and even RPAbased methods fail to predict this degeneracyboth versions of vdW-DF either predict a difference of 0.6 kcal/mol (20%) at the true equilibrium geometries 36 or overestimate the binding distances by as much as 0.5 Å; 265 the error of the pairwise TS method on the PD conformation is 0.8 kcal/mol, 50 and all RPA-derived methods reviewed in Section 4.5 overbind the PD conformation by ∼0.7 kcal/mol. 148 In contrast, the MBD method, which explicitly accounts for the intra-and Figure 7.…”

Section: Benchmark Databasesmentioning

confidence: 99%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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Noncovalent van der Waals (vdW) or dispersion forces are ubiquitous in nature and influence the structure, stability, dynamics, and function of molecules and materials throughout chemistry, biology, physics, and materials science. These forces are quantum mechanical in origin and arise from electrostatic interactions between fluctuations in the electronic charge density. Here, we explore the conceptual and mathematical ingredients required for an exact treatment of vdW interactions, and present a systematic and unified framework for classifying the current first-principles vdW methods based on the adiabatic-connection fluctuation−dissipation (ACFD) theorem (namely the Rutgers−Chalmers vdW-DF, Vydrov−Van Voorhis (VV), exchange-hole dipole moment (XDM), Tkatchenko−Scheffler (TS), many-body dispersion (MBD), and random-phase approximation (RPA) approaches). Particular attention is paid to the intriguing nature of many-body vdW interactions, whose fundamental relevance has recently been highlighted in several landmark experiments. The performance of these models in predicting binding energetics as well as structural, electronic, and thermodynamic properties is connected with the theoretical concepts and provides a numerical summary of the state-of-the-art in the field. We conclude with a roadmap of the conceptual, methodological, practical, and numerical challenges that remain in obtaining a universally applicable and truly predictive vdW method for realistic molecular systems and materials.

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Binding energies in benzene dimers: Nonlocal density functional calculations

Cited by 158 publications

References 45 publications

Vibration–rotation-tunneling states of the benzene dimer: an ab initio study

Vibration–rotation-tunneling states of the benzene dimer: an ab initio study

Modeling π–π Interactions with the Effective Fragment Potential Method: The Benzene Dimer and Substituents

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

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