In the pursuit of small “red shift” of C–H stretching vibrational frequency of C–H⋯π interactions for benzene dimer: How to amend MP2 calculations to reproduce the experimental results

Dinadayalane, T. C.; Leszczyński, Jerzy

doi:10.1063/1.3085815

Cited by 26 publications

(17 citation statements)

References 29 publications

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“…556 Ideally, the characterization of intermolecular interactions, in particular dihydrogen bonds formed by multiple sites either of donors or acceptors of protons or any other ones can be performed by computing the molecular charge density, according to which the explanation of the cooperative effect related to molecular energy becomes possible 557,558 besides the elucidation of the dynamism of the infrared vibrational modes, e.g., the redshifts on the stretch frequencies of the proton donors. [559][560][561][562][563][564][565][566] The questions regarding the red-and blue-shifting hydrogen bonds are debated constantly in the literature. [567][568][569][570][571][572][573][574] One of the most important topics is the presentation of new theoretical approaches, such as the analysis of the induced dipole proposed by Hermansson 575 for investigating the origin of the vibrational blue shift.…”

Section: The Use Of the Qtaim Topology For Intermolecular Modellingmentioning

confidence: 99%

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Oliveira

2013

Phys. Chem. Chem. Phys.

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In this paper, the intermolecular structural study asserted by the vibrational analysis in the stretch frequencies of hydrogen bonds (π···H) and dihydrogen bonds (H(-δ)···H(+δ)) have definitively been revisited by means of calculations carried out by Density Functional Theory (DFT) and topological parameters derived from the classic treatise of the Quantum Theory of Atoms in Molecules (QTAIM). As a matter of fact the π···H hydrogen bond is formed between the hydrofluoric acid and the C≡C bond of the acetylene, but the QTAIM calculations revealed a distortion in this interaction due to the formation of the ternary complex C(2)H(2)···2(HF). Although the π bonds of ethylene (C(2)H(4)), propylene (C(2)H(3)(CH(3))), and t-butylene (C(2)H(2)(CH(3))(2)) are considered proton acceptors, two hydrogen-bond types--π···H and C···H--can be observed. Over and above the analysis of the π hydrogen bonds, theoretical arguments also were used to discuss the red-shifts in the stretch frequencies of the binary dihydrogen complexes formed by BeH(2)···HX with X = F, Cl, CN, and CCH. Although a vibrational blue-shift in the stretch frequency of the H-C bond of HCF(3) due to the formation of the BeH(2)···HCF(3) dihydrogen complex was obtained, unmistakable red-shifts were detected in LiH···HCF(3), MgH(2)···HCF(3), and NaH···HCF(3). Moreover, the alkali-halogen bonds were identified in relation to the formation of the trimolecular systems NaH···2(HCF(3)) and NaH···2(HCCl(3)). At last, theoretical calculations and QTAIM molecular integrations were used to study a novel class of dihydrogen-bonded complexes (mC(2)H(5)(+)···nMgH(2) with m = 1 or 2 and n = 1 or 2) based in the insight that MgH(2) can bind with the non-localized hydrogen H(+δ) of the ethyl cation (C(2)H(5)(+)). In an overview, QTAIM calculations were applied to evaluate the molecular topography, charge density, as well as to interpret the shifted frequencies either to red or blue caused by the formation of the hydrogen bonds and dihydrogen bonds.

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Section: The Use Of the Qtaim Topology For Intermolecular Modellingmentioning

confidence: 99%

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Oliveira

2013

Phys. Chem. Chem. Phys.

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“…Recently, there has been significant interest in understanding of CÀHÁ Á Áp, NÀHÁ Á Áp, and OÀHÁ Á Áp interactions involving benzene and substituted benzene systems [12][13][14][15][16], and the computed characteristic vibrational spectra for those complexes have been reported to be in a good agreement with the experimental results [13][14][15][16]. Modifications of host molecules by altering shapes have been used in designing of novel ionophores, new drug targets as well as in re-optimizing chemical agents that could be of medicinal value [1,[17][18][19].…”

Section: Introductionmentioning

confidence: 99%

The effect of ring annelation to benzene on cation-π interactions: DFT study

Dinadayalane

Hassan

Leszczyński

2010

Journal of Molecular Structure

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“…These results, too, are in agreement with the experimentally observed red-shift of 3 cm −1 for these modes and also theoretical calculations of the vibrational spectra for the T-shape structure. [36][37][38] FIG. 2.…”

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Communication: Benzene dimer—The free energy landscape

Tummanapelli

Vasudevan

2013

The Journal of Chemical Physics

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Establishing the relative orientation of the two benzene molecules in the dimer has remained an enigmatic challenge. Consensus has narrowed the choice of structures to either a T-shape, that may be tilted, or a parallel displaced arrangement, but the relatively small energy differences makes identifying the global minimum difficult. Here we report an ab initio Car-Parrinello Molecular Dynamics based metadynamics computation of the free-energy landscape of the benzene dimer. Our calculations show that although competing structures may be isoenergetic, free energy always favors a tilted T-shape geometry at all temperatures where the bound benzene dimer exist.

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In the pursuit of small “red shift” of C–H stretching vibrational frequency of C–H⋯π interactions for benzene dimer: How to amend MP2 calculations to reproduce the experimental results

Cited by 26 publications

References 29 publications

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

The effect of ring annelation to benzene on cation-π interactions: DFT study

Communication: Benzene dimer—The free energy landscape

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In the pursuit of small “red shift” of C–H stretching vibrational frequency of C–H⋯π interactions for benzene dimer: How to amend MP2 calculations to reproduce the experimental results

Cited by 26 publications

References 29 publications

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H−δ⋯H+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H−δ⋯H+δdihydrogen bonds

The effect of ring annelation to benzene on cation-π interactions: DFT study

Communication: Benzene dimer—The free energy landscape

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Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds