Dispersion Energy from Density-Functional Theory Description of Monomers

Misquitta, Alston J.; Jeziorski, Bogumił; Szalewicz, Krzysztof

doi:10.1103/physrevlett.91.033201

Cited by 360 publications

(431 citation statements)

References 34 publications

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“…38 The ab initio method used was SAPT(DFT): symmetry-adapted perturbation theory (SAPT) based on monomer wave functions, orbital energies, and response properties obtained from (time-dependent) DFT calculations. This method, initially proposed by Williams and Chabalowski, 63 was later extended and implemented by Misquitta et al [64][65][66] and by Heßelmann et al 37,67,68 It is much more economical than the regular SAPT 69 or the coupledcluster method using single, double, and perturbative triple excitations, CCSD(T), the two approaches that have established themselves currently as the most accurate of practically applicable methods for obtaining intermolecular interaction potentials. Both groups have shown that SAPT(DFT) results for the benzene dimer are about as accurate as the results from CCSD(T).…”

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.

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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.

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152

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“…These calculations were performed using the DALTON 2.0 program. 36 For deeper insight into the nature of the interaction energies we have additionally used the CamCASP program 37 to perform symmetry adapted perturbation theory (SAPT) DFT [38][39][40] calculations to decompose the interaction energies into physical components. Fig.…”

Section: Beyond the Pbe Functional A Calculations For Molecularmentioning

confidence: 99%

High pressure ionic and molecular crystals of ammonia monohydrate within density functional theory

Griffiths¹,

Misquitta²,

Fortes

et al. 2012

The Journal of Chemical Physics

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The following article has been submitted to The Journal of Chemical Physics. After it is published, it will be found at http://jcp.aip.org/ A combination of first-principles density functional theory calculations and a search over structures predicts the stability of a proton-transfer modification of ammonia monohydrate with space group P 4/nmm. The phase diagram is calculated with the PBE density functional, and the effects of a semi-empirical dispersion correction, zero point motion, and finite temperature are investigated.Comparison with MP2 and coupled cluster calculations shows that the PBE functional over-stabilizes proton transfer phases because too much electronic charge moves with the proton. This over-binding is partially corrected by using the PBE0 hybrid exchange-correlation functional, which increases the enthalpy of P 4/nmm by about 0.6 eV per formula unit relative to phase I of ammonia monohydrate (AMH-I) and shifts the transition to the proton transfer phase from the PBE pressure of 2.8 GPa to about 10 GPa. This is consistent with experiment as proton transfer phases have not been observed at pressures up to ∼9 GPa, while higher pressures have not yet been explored experimentally.

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“…Ref. 31 for an equivalent route to DFT-SAPT dispersion energies͒ which were also used to determine its exchange correction. The PBE0AC xc-potential, introduced and defined in Ref.…”

Section: A Dft-sapt Calculationsmentioning

confidence: 99%

New CO–CO interaction potential tested by rovibrational calculations

Vissers

Heßelmann

Jansen

et al. 2005

The Journal of Chemical Physics

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A four-dimensional potential energy surface ͑PES͒ for the CO dimer consisting of rigid molecules has been calculated, using a scheme that combines density functional theory to describe the monomers and symmetry adapted perturbation theory for the interaction energy ͑DFT-SAPT͒. The potential is fitted in terms of analytic functions, and the fitted potential is used to compute the lowest rovibrational states of the dimer. The quality of the PES is comparable to that of a previously published surface ͓G. W. M. Vissers, P. E. S. Wormer, and A. van der Avoird, Phys. Chem. Chem. Phys., 5, 4767 ͑2003͔͒, which was calculated with the coupled cluster single double and perturbative triples ͓CCSD͑T͔͒ method. It is shown that a weighted average of the DFT-SAPT and the CCSD͑T͒ potential gives results that are in very good agreement with experimental data, for both ( 12 CO) 2 and ( 13 CO) 2 . The relative weight was determined by adjusting the energy gap between the origins of the lowest two stacks of rotational levels of ( 12 CO) 2 to the measured value.

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Dispersion Energy from Density-Functional Theory Description of Monomers

Cited by 360 publications

References 34 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

High pressure ionic and molecular crystals of ammonia monohydrate within density functional theory

New CO–CO interaction potential tested by rovibrational calculations

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