Properties of some weakly bound complexes obtained with various density functionals

García, Antón; Cruz, Elso Manuel Cruz; Sarasola, C.; Ugalde, Jesús M.

doi:10.1016/s0166-1280(96)04948-2

Cited by 6 publications

(12 citation statements)

References 18 publications

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“…16,18,22 The hybrid functionals along with the MP2 method give values a bit larger but still underestimated with respect to the experimental value. However, the basis set has a noticeable effect on the optimum intermolecular distance.…”

Section: Resultsmentioning

confidence: 94%

“…With respect to the intermolecular distance, in general, the pure functionals yield values that are too short, as found for similar bπ‚aσ charge-transfer complexes. 16,18,22 The hybrid functionals along with the MP2 method give values a bit larger but still underestimated with respect to the experimental value. However, the basis set has a noticeable effect on the optimum intermolecular distance.…”

Section: Resultsmentioning

confidence: 94%

“…Note that all the density functional calculations have been carried out with a slightly modified Becke's correction term, 19 which has been found to yield improved results for both strongly bound molecules 21 and weakly bound complexes. 18,22 In general, it is observed that the approximate pure functionals BP86 and BPW91 describe poorly the geometrical parameters and hence do not reproduce the rotational constants satisfactorily. Remarkably, the BLYP method does yield very good estimates for the rotational constants, irrespective of the basis set used.…”

Section: Discussionmentioning

confidence: 99%

“…22 Although it has been shown 22 that the 6-311++G(d,p) basis set 23 represents a reasonable compromise between computational cost and accuracy, we have carried out an additional set of calculations with the larger cc-pVTZ basis set, 24 which includes f-type functions for all the elements considered. Consequently, all the calculations presented in this paper have been carried out with the 6-311++G(d,p) and cc-pVTZ basis sets, with a locally modified version of the Gaussian94/DFT suite of programs, 25 which incorporates the above-mentioned modification in the Becke's exchange functional.…”

Section: Methodsmentioning

confidence: 99%

“…We have recently shown that a slight modification 19 of the Becke's gradient correction term to the exchange functional yields a noticeably improved performance of the so-called B3LYP hybrid method 20 for the calculated properties of both the G2 set of molecules 21 and some selected charge-transfer and hydrogen-bonded complexes. 22 Although it has been shown 22 that the 6-311++G(d,p) basis set 23 represents a reasonable compromise between computational cost and accuracy, we have carried out an additional set of calculations with the larger cc-pVTZ basis set, 24 which includes f-type functions for all the elements considered. Consequently, all the calculations presented in this paper have been carried out with the 6-311++G(d,p) and cc-pVTZ basis sets, with a locally modified version of the Gaussian94/DFT suite of programs, 25 which incorporates the above-mentioned modification in the Becke's exchange functional.…”

Section: Methodsmentioning

confidence: 99%

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Density Functional Studies of the n·aσ Charge-Transfer Complex between Sulfur Dioxide and Chlorine Monofluoride

1998

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The n‚aσ charge-transfer complex formed by sulfur dioxide and chlorine monofluoride has been studied with various approximate pure and hybrid density functional methods and the second-order Moller-Plesset (MP2) theory. The calculations demonstrate that one pure method and one hybrid method, namely, the so-called BLYP and BHHLYP, respectively, lead to reasonably good estimates of the experimentally measured rotational constants. However, the predicted BHHLYP intermolecular distance is found to be noticeably closer to the experimental value. Our best estimation for the intermolecular interaction energy is 1.93 kcal/mol. We have also been able to calculate the number and energies of the vibrational states supported by the intermolecular stretching mode. Only 11 such states have been found. The performance of the various approximate density functionals and the MP2 theory is compared and discussed. Finally, we comment on the analysis of the natural bond orbitals, which has been found to be very valuable to shed light on the nature of weak intermolecular interactions.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 94%

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 3 more Smart Citations

Density Functional Studies of the n·aσ Charge-Transfer Complex between Sulfur Dioxide and Chlorine Monofluoride

1998

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Density functional studies of the n·aσ charge-transfer complexes between NH 3 and BrX (X=Cl, Br)

García

Elorza

Ugalde

2000

Journal of Molecular Structure: THEOCHEM

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Characterization of Competing Halogen- and Hydrogen-Bonding Motifs in Simple Mixed Dimers of HCN and HX (X = F, Cl, Br, and I)

Perkins

Tschumper

2022

J. Phys. Chem. A

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This work performs the first systematic comparison of hydrogen-and halogen-bonded configurations of the HCN/HX mixed dimer, where X = F, Cl, Br, and I. Eleven different minima have been characterized for these four heterogeneous dimers near the CCSD(T) complete basis set (CBS) limit. For each complex, two different hydrogen-bonded minima were identified: the global minimum where HX acts as the hydrogen bond donor and a local minimum where HX acts as the hydrogen bond acceptor. A halogenbonded local minimum was also identified for all but the fluorine mixed dimer. To the best of our knowledge, three of the minima are identified here for the first time. The hydrogen-and halogen-bonded local minima of each complex become more energetically competitive with the global minimum as the atomic radius of the halogen atom increases. CCSD(T) relative energies of the hydrogen-bonded local minima computed near the CBS limit decrease from 4.5 kcal mol −1 for HCN/HF to 2.9, 2.4, and 1.2 kcal mol −1 for X = Cl, Br, and I, respectively. Corresponding relative energies for the halogen-bonded local minima range from 4.0 kcal mol −1 for X = Cl to 2.7 kcal mol −1 for X = Br and to as little as 0.5 kcal mol −1 X = I. Harmonic vibrational frequency shifts reported here suggest that it may be feasible to differentiate between the various minima for X = Cl, Br, and I via spectroscopic analysis, as was the case for the HCN/HF dimer.

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Properties of some weakly bound complexes obtained with various density functionals

Cited by 6 publications

References 18 publications

Density Functional Studies of the n·aσ Charge-Transfer Complex between Sulfur Dioxide and Chlorine Monofluoride

Density Functional Studies of the n·aσ Charge-Transfer Complex between Sulfur Dioxide and Chlorine Monofluoride

Density functional studies of the n·aσ charge-transfer complexes between NH 3 and BrX (X=Cl, Br)

Characterization of Competing Halogen- and Hydrogen-Bonding Motifs in Simple Mixed Dimers of HCN and HX (X = F, Cl, Br, and I)

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