Tunnelling splittings in the high resolution microwave and UV spectra of the benzonitrile—water complex: modelling the internal motion in its S<sub>0</sub>and S<sub>1</sub>states

Schäfer, Martin; Borst, David R.; Pratt, David W.; Brendel, K.

doi:10.1080/00268970210162754

Cited by 15 publications

(19 citation statements)

References 25 publications

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“…The observed structure of the phenylacetylene-water complex, PW3, is similar to the structure of the benzonitrile-water complex. [63][64][65] Ishikawa et al have reported the FDIR spectrum of the benzonitrile-water complex, which shows two transitions in the OÀH stretching region at 3614 and 3727 cm À1 corresponding to the hydrogen-bonded and free OÀH vibrations, respectively. [63] Comparison of the shifts in the OÀH stretching frequencies of the water complexes with phenylacetylene and benzonitrile suggests that the stability of the phenylacetylenewater complex is lower than the benzonitrile-water complex.…”

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confidence: 98%

Phenylacetylene: A Hydrogen Bonding Chameleon

et al. 2010

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Molecules with multiple hydrogen bonding sites offer the opportunity to investigate competitive hydrogen bonding. Such an investigation can become quite interesting, particularly when the molecule of interest has neither lone-pair electrons nor strongly acidic/basic groups. Phenylacetylene is one such molecule with three hydrogen bonding sites that cannot be ranked into any known hierarchical pattern. Herein we review the structures of several binary complexes of phenylacetylene investigated using infrared optical double-resonance spectroscopy in combination with high-level ab initio methods. The diversity of intermolecular structures formed by phenylacetylene with various reagents is remarkable. The nature of intermolecular interaction with various reagents is the result of a subtle balance between various configurations and competition between the electrostatic and dispersion energy terms, while trying to maximize the total interaction strength.

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confidence: 98%

Phenylacetylene: A Hydrogen Bonding Chameleon

et al. 2010

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“…As we have discussed earlier, the fluorine lone pair electron density in Still, the strength of any hydrogen bond depends more on donor acidity than on acceptor basicity, an effect that is nicely confirmed by comparisons of the properties of pDFB and BN water complexes. The V 2 barriers in the BN-water are nearly the same in both states [65]. There are obviously only very small changes in the electronic structure of BN upon excitation, which is also indicated by a small increase of its dipole moment (+0.09 D) [73].…”

Section: A5 Water Complexesmentioning

confidence: 66%

“…Concerning the pDFBW, the magnitude of its inertial defects are relatively small (ΔI″ = -0. 68 It is interesting to compare the results for pDFBW to those for the analogous benzonitrilewater (BNW) complex [62][63][64][65]. In both complexes, the oxygen is bound to an ortho hydrogen and one hydroxy hydrogen is bound to the fluorine or the cyano group.…”

Section: A5 Water Complexesmentioning

confidence: 99%

“…The differences between the rotational constants of two subbands are calculated from ΔA″ = A v0 ″ -A v1 ″, ΔA′ = A v0 ′ -A v1 ′ and so forth [66]. According to Table 7 As discussed in the analysis of the tunneling splitting in BNW [65], there exist several possible models for the motion of the attached water molecule. All require the breaking and remaking of at least one of the hydrogen bonds ( F---H-O or H---O-H ).…”

Section: A5 Water Complexesmentioning

confidence: 99%

“…with respect to that of BN itself [65] More specific Information about the motion of the water molecule in pDFBW comes from an analysis of the observed tunneling splitting of 3.63 GHz. Also, each of the subbands has slightly different rotational constants due to the coupling between torsional motion of water and overall rotation.…”

Section: A5 Water Complexesmentioning

confidence: 99%

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Structures, charge distributions, and dynamical properties of weakly bound complexes of aromatic molecules in their ground and electronically excited states

Kang¹,

Pratt²

2005

International Reviews in Physical Chemistry

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Abstract.Complexes or clusters are non-covalently bound assemblies of two or more molecules that are held together by hydrogen bonding, van der Waals interactions, and other weak forces. The derived values of the rotational constants can be used to determine the structures of such species, in both their ground and electronically excited states. Some species exhibit different structures in the two states, owing to photon-induced changes in their electronic distributions. Evidence for the motion of one species relative to another along some intermolecular coordinate also is observed in some cases. We describe the application of these techniques to nitrogen and water complexes of p-difluorobenzene and Ar and water complexes of indole and azaindole, as models of hydrophobic and hydrophilic interactions. These studies have provided detailed information about how the electronic charge distributions of the species interact, how the structures of the individual species are modified when they interact, and how the properties of the complex are different from its component parts.iv

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Electronic Spectroscopy in the Gas Phase

Pratt

2011

Handbook of High‐resolution Spectroscopy

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A frequency‐doubled continuous wave (CW) ring dye laser, operating in the ultraviolet (UV), has been combined with a molecular beam machine and rapid data acquisition methods to obtain the electronic spectra of several large polyatomic molecules and their weakly bound complexes at unparalleled spectral resolution, approaching one part in 10 9 . Thus revealed for the first time are the underlying molecular eigenstates of isolated molecules, which provide unique information about their structures and dynamical behavior in both ground and excited electronic states. Light‐induced changes in the electronic charge distributions of different electronic states, with or without the attached solvent molecules, are revealed by studies of these spectra in applied electric fields (the Stark effect). Potential applications of the method to small biological molecules are discussed.

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Tunnelling splittings in the high resolution microwave and UV spectra of the benzonitrile—water complex: modelling the internal motion in its S₀and S₁states

Cited by 15 publications

References 25 publications

Phenylacetylene: A Hydrogen Bonding Chameleon

Phenylacetylene: A Hydrogen Bonding Chameleon

Structures, charge distributions, and dynamical properties of weakly bound complexes of aromatic molecules in their ground and electronically excited states

Electronic Spectroscopy in the Gas Phase

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Tunnelling splittings in the high resolution microwave and UV spectra of the benzonitrile—water complex: modelling the internal motion in its S0and S1states

Cited by 15 publications

References 25 publications

Phenylacetylene: A Hydrogen Bonding Chameleon

Phenylacetylene: A Hydrogen Bonding Chameleon

Structures, charge distributions, and dynamical properties of weakly bound complexes of aromatic molecules in their ground and electronically excited states

Electronic Spectroscopy in the Gas Phase

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Product

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Tunnelling splittings in the high resolution microwave and UV spectra of the benzonitrile—water complex: modelling the internal motion in its S₀and S₁states