Rotational spectrum, dynamics, and bond energy of the floppy dimethylether⋯neon van der Waals complex

Maris, Assimo; Camináti, Walther

doi:10.1063/1.1533012

Cited by 27 publications

(27 citation statements)

References 20 publications

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“…However, they give a first estimate of the position of the noble gas atom. Both a and 180 À a values are consistent with the experimental data, but, as for DME ± Ar [5] and DME ± Ne, [6] the former value, for which the noble gas atom is tilted towards the oxygen atom, was chosen. A method for estimating r e is described below.…”

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confidence: 92%

“…[1,2] SAMs have many potential applications in modern technology, including chemical sensing, [3±5] control of surface properties such as wettability and friction, [6,7] corrosion protection [8] and, in recent times, the nanofabrication of electronic components. [9] Among the most well-known and studied SAMs are thiols on gold, [1,2,10,11] and organosilanes on silicon.…”

Section: Introductionmentioning

confidence: 99%

“…The best method is to use splittings of the rotational lines due to tunnelling between equivalent minima in the potential energy surface (see, for example, refs. [5,6]). Alternative data, such as centrifugal distortion constants [11] or shifts of rotational constants on going from the free molecule to the adduct, [12] have been often used.…”

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confidence: 97%

“…DME 3DME ± Ne [a] DME 3DME ± Ar [b] DME 3DME ± Kr [c] DME 3DME ± Xe [d] DM [a] ref. [6]; [b] ref. [5]; [c] ref.…”

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confidence: 99%

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Adducts of Xenon with Organic Molecules: Rotational Spectrum of Dimethyl Ether–Xe

et al. 2003

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KEYWORDS:gas-phase reactions ¥ noble gases ¥ rotational spectroscopy ¥ van der Waals adducts ¥ xenon Considerable interest has been devoted during the last two decades to the investigation of the rather unusual ™chemical compounds∫ formed by the combination of a noble gas atom with an organic molecule.[1] Various spectroscopic methods have been used to observe these adducts in the plume following a supersonic expansion.[2] Many van der Waals adducts between a noble gas atom and a cyclic organic molecule have been investigated by rotationally resolved spectroscopy, but only a very few involve a Xe atom: benzene ± Xe [3] and oxirane ± Xe [4] . The lack of experimental data on this kind of Xe complexes is probably due to the mass of Xe, which makes the rotational constants of its van der Waals complexes smaller than those of complexes of the lighter noble gases, and the large number of isotopes, with a maximum of natural abundance (27 %) for 132 Xe. Both factors considerably reduce the intensities of the rotational lines.Due to the higher polarizability of Xe relative to lighter noble gases, a larger dispersion ± energy interaction is expected for complexes with Xe. Here, we compare the stability and the dynamics of the noble gas atom in dimethyl ether ± xenon (DME ± Xe) to those of the related adduct oxirane ± Xe [4] and of the complexes of DME with Ne, Ar, and Kr, whose jet-cooled rotational spectra have been observed.[5±7] Figure 1 shows DME ± Xe and the van der Waals structural parameters.The first estimates of the rotational constants of the DME ± Xe were obtained by placing the xenon atom at a distance of 3.82 ä from the center of mass (CM) of DME, lying along the c axis of DME, but shifted by about 158 towards the oxygen atom, in a geometrical arrangement similar to that found for DME ± Ar [5] and DME ± Kr.[7] The r 0 geometry of DME [8] was assumed to Figure 1. Schematic diagram of DME ± Xe with van der Waals structural parameters.remain unaltered in the complex. On going from the molecule to the adduct the directions of the principal axes of inertia with respect to the C-O-C skeleton change, so that the m b -type spectrum of DME changes to a predominantly m c -type spectrum in the adduct (Figure 2). Figure 2. Switching of principal axes on going from DME to DME ± Xe.The rotational spectra of the two most abundant isotopic species, with 132 Xe and 129 Xe (ca. 27 and 26 % natural abundance, respectively), were investigated. Several high-J high-K a m c -R-type lines, doubly overlapping due to the near-prolate behaviour of K a , were easily assigned; later, the weaker lines with lower K a values, resolved into asymmetry doublets, were measured. The experimental frequencies (Table 1) were fitted with the Watson quartic Hamiltonian.[9] Since DME ± Xe is a near-prolate top, the S reduction and the I r representation were chosen. Three quartic centrifugal distortion parameters D J , D JK and D K were determined from the fit. The spectroscopic constants obtained are listed for both isotopomers in Table 2 together w...

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confidence: 92%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 97%

“…DME 3DME ± Ne [a] DME 3DME ± Ar [b] DME 3DME ± Kr [c] DME 3DME ± Xe [d] DM [a] ref. [6]; [b] ref. [5]; [c] ref.…”

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Adducts of Xenon with Organic Molecules: Rotational Spectrum of Dimethyl Ether–Xe

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“…This is the case, for example, of complexes of pyridine with all RG atoms, that is, RG = He, [2] Ne, [3] Ar, [4] Kr, [4a] or Xe. [5] Alternatively, when a RG atom is linked to an open-chain molecule, such as, for example, dimethyl ether, all complexes, for RG = Ne, [6] Ar, [7] Kr, [8] and Xe, [9] display rotational transitions characterized by inversion splittings. From centrifugal distortion effects, it has been possible to estimate the dissociation energies of the complexes, which are higher for the aromatic molecules complexes and increase with the atomic number of RG.…”

Section: Introductionmentioning

confidence: 99%

Rotational Spectrum and Internal Dynamics of Tetrahydrofuran–Krypton

et al. 2011

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The rotational spectrum of the tetrahydrofuran-krypton van der Waals complex has been investigated by pulsed-jet Fourier transform microwave spectroscopy. The spectra of the (84)Kr and (86)Kr isotopologues have been assigned and the krypton atom is located nearly over the oxygen atom, almost perpendicular to the COC plane. Each rotational transition is split into two component lines due to, according to the observed Coriolis coupling term between the tunneling states, the residual pseudorotational effects of the ring in the complex. The splitting between the two vibrational sublevels is 87.462(2) and 87.062(2) MHz for the (84)Kr and (86)Kr isotopologues, respectively. These splittings have been used to determine the barrier to inversion, B(2) = 67 cm(-1). The dissociation energy has been estimated to be 3.7 kJ mol(-1) from centrifugal distortion effects.

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Theoretical investigation of hydrogen bonding in lactonitrile–water complexes

Rivelino

Canuto

2005

Int J of Quantum Chemistry

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ABSTRACT:Møller-Plesset perturbation and density functional theories were applied to study the relative strength of the H-bonds formed in different sites (OH, CN, and CH) of lactonitrile with water. Three lactonitrile-water complexes (termed I, II, and III) were located. Then structures, binding energies, and changes in their vibrational frequencies were calculated using the MP2 method and the B3PW91 functional with the 6-311ϩϩG(2df,2p) basis set. The binding energies were corrected for the basis set superposition errors and zero-point vibration energies. At the MP2 level the corrected binding energy of the most strongly bonded Complex I was calculated to be 6.5 kcal/ mol, whereas it is only 2.9 kcal/mol for the Complex II. The CH . . . O hydrogen-bonded Complex III was found to have a very small binding energy between 1.5 and 2 kcal/ mol.

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Rotational spectrum, dynamics, and bond energy of the floppy dimethylether⋯neon van der Waals complex

Cited by 27 publications

References 20 publications

Adducts of Xenon with Organic Molecules: Rotational Spectrum of Dimethyl Ether–Xe

Adducts of Xenon with Organic Molecules: Rotational Spectrum of Dimethyl Ether–Xe

Rotational Spectrum and Internal Dynamics of Tetrahydrofuran–Krypton

Theoretical investigation of hydrogen bonding in lactonitrile–water complexes

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