Investigation of the benzene-dimer potential energy surface: DFT/CCSD(T) correction scheme

Bludský, Ota; Rubeš, Miroslav; Soldán, Pavel; Nachtigall, Petr

doi:10.1063/1.2890968

Cited by 182 publications

(216 citation statements)

References 49 publications

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“…In ref. 45, the energy of this characteristic point was found to be lower than that of the S3 structure, but the importance of this finding for tunneling pathways was not realized. In contrast, in ref.…”

Section: B Characteristic Points On the Potential Energy Surfacementioning

confidence: 78%

“…Interestingly, the S3a structure was also found in ref. 45 and 48, but was interpreted as a S4-type structure. In ref.…”

Section: B Characteristic Points On the Potential Energy Surfacementioning

confidence: 99%

“…48 the energy of the S3a point was higher than that of S3, and the S3 saddle point was of index 1 (the authors of ref. 45 did not publish the indices of their stationary points). More detailed information on the stationary points of our potential surface can be found in the ESI.w…”

Section: B Characteristic Points On the Potential Energy Surfacementioning

confidence: 99%

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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: B Characteristic Points On the Potential Energy Surfacementioning

confidence: 78%

“…Interestingly, the S3a structure was also found in ref. 45 and 48, but was interpreted as a S4-type structure. In ref.…”

Section: B Characteristic Points On the Potential Energy Surfacementioning

confidence: 99%

See 1 more Smart Citation

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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show abstract

“…256−263 In particular, the fine balance between the Pauli repulsion, electrostatic (quadrupole−quadrupole) interactions, and vdW dispersion results in an intricate potential energy surface (PES) with many local minima. 264 The nearly degenerate T-shaped and parallel-displaced (PD) conformations of the benzene dimer are contained in both S22 and S66 sets, but whether a particular method reproduces this degeneracy is naturally not reflected in the corresponding statistical errors. Another reason why these two geometries are particularly interesting is precisely the fact that they are two probes of the same PES and hence the number of potential sources of error in their description is limited.…”

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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“…In chemical studies, benzene is used as a useful substance including as a solvent or also as a precursor of many synthetic materials, and so on [1]. While some works studied mono-benzene or multibenzene molecules solely [2,3], yet others considered benzene rings with hetero-atoms or hetero-molecules [4,5]. Among all hetero-atoms, we have selected boron and nitrogen as two atoms on both sides of carbon atom in periodic table with difference of one electron less and more than the number of valence electrons in carbon, respectively.…”

Section: Introductionmentioning

confidence: 99%

The structural properties of boron and nitrogen adsorption on benzene molecule: a density functional study

Hoseini

Faizabadi

2015

J Theor Appl Phys

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The structural properties of boron and nitrogen atoms added on benzene (Bz) molecule are studied using density functional theory within Gaussian 03 program package. The adsorption energy, HOMO-LUMO energy gap (D H-L ) and also the optimized bond lengths (C-C and C-H bond lengths) of the structures are evaluated. In this work, three adsorption sites for both boron and nitrogen were selected, hollow site (H), middle site (M) and top site (T), as their initial positions. It is found that for boron adsorption on Bz molecule, the relaxed middle site configuration has the most stable geometry, while in NBz, we obtained similar positions after optimization process. We have also illustrated that the relaxed NBz positions are in higher stability than the relaxed BBz positions. As a consequence, it is found that the stability of an isolated benzene molecule increases by adding boron or nitrogen on top of it.

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Investigation of the benzene-dimer potential energy surface: DFT/CCSD(T) correction scheme

Cited by 182 publications

References 49 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

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

The structural properties of boron and nitrogen adsorption on benzene molecule: a density functional study

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