Spectroscopic evidence for proton transfer within the bimolecular complex hydrogen iodide-ammonia trapped in cryogenic matrixes

Schriver, L.; Schriver, A.; Perchard, J. P.

doi:10.1021/ja00350a017

Cited by 29 publications

(27 citation statements)

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“…spectra of the complexes formed between amines and hydrogen halides have recently been extensively investigated using the matrix isolation technique. [19][20][21][22][23][24][25] Where there are no gas-phase spectroscopic data, as in the case of strongly hydrogen-bonded systems, a study of the complex isolated in an inert matrix, such as argon, provides the best available approach to the gas-phase complex. For these complexes in argon matrices the extent of proton transfer was found to increase from ammonia-hydrogen chloride through ammonia-hydrogen bromide or methylamine-hydrogen chloride (where the proton is more or less equally shared between the nitrogen and halogen) to trimethylamine-hydrogen iodide (where the proton is substantially transferred to the amine).…”

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confidence: 99%

Infrared matrix isolation studies of complexes between N,N-dimethylacetamide and hydrogen halides. Part 1.—Hydrogen chloride and hydrogen bromide complexes

Mielke¹,

Barnes²

1986

J. Chem. Soc., Faraday Trans. 2

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Infrared spectra are reported of strongly hydrogen-bonded 1 : 1 and 1: 2 complexes of N, N-dimethylacetamide with hydrogen chloride or hydrogen bromide in argon and nitrogen matrices. In the 1 : 1 complexes, the proton is more or less equally shared between the oxygen and halogen atoms with little change in the extent of proton transfer between argon and nitrogen matrices (unlike the amine-hydrogen halide complexes). The second hydrogen halide molecule in the 1 : 2 complexes appears to form a hydrogen bond with the nitrogen atom of the amide.

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confidence: 99%

Infrared matrix isolation studies of complexes between N,N-dimethylacetamide and hydrogen halides. Part 1.—Hydrogen chloride and hydrogen bromide complexes

Mielke¹,

Barnes²

1986

J. Chem. Soc., Faraday Trans. 2

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“…However, the vibrational spectra for the NH 3 -HCl and related hydrogen-bonded dimers trapped in nitrogen and rare-gas matrices have been intensively studied for quite some time. [5][6][7][8][9][10][11][12][13][14]20 From this previous work, particularly Refs. 12-14 and 20, it is clear that there is considerable interaction between the dimer and the rare gas matrix in which it is trapped, leading to a significant shift in the vibrational frequency of the H-Cl stretch relative to its gas-phase value.…”

Section: Resultsmentioning

confidence: 93%

“…Before discussing the vibrational frequencies it is appropriate to compare the DFT structure and binding energies calculated here with previous work since it is well-known that DFT overestimates the hydrogen bond strength in the dimer. The structure of the NH 3 -HCl dimer in the gas-phase was established using rotational spectroscopy quite early by Legon et al, 32,33 and numerous experimental [5][6][7][8][9][10][11][12][13][14] and theoretical 14-20 studies have been reported. We summarize these in Table I.…”

Section: Resultsmentioning

confidence: 99%

“…the ionic and orbital dynamics affects calculations of the vibrational frequency. We select the NH 3 -HCl dimer as the system to investigate because there is a considerable amount of previous work on this and closely related systems, and the vibrational frequencies have been investigated extensively, both experimentally [5][6][7][8][9][10][11][12][13][14] and theoretically. [14][15][16][17][18][19][20] In particular the influence of the anharmonic effects upon the vibrational frequency has been intensively studied, although the magnitude of the vibrational frequency shift due to anharmonic effects is still not clearly established, at least for the gas-phase dimer.…”

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confidence: 99%

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Ion-orbital coupling in Car-Parrinello calculations of hydrogen-bond vibrational dynamics: Case study with the NH3–HCl dimer

Ong¹,

Lee²,

Kang³

2011

The Journal of Chemical Physics

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We have performed Car-Parrinello molecular dynamics (CPMD) calculations of the hydrogen-bonded NH(3)-HCl dimer. Our main aim is to establish how ionic-orbital coupling in CPMD affects the vibrational dynamics in hydrogen-bonded systems by characterizing the dependence of the calculated vibrational frequencies upon the orbital mass in the adiabatic limit of Car-Parrinello calculations. We use the example of the NH(3)-HCl dimer because of interest in its vibrational spectrum, in particular the magnitude of the frequency shift of the H-Cl stretch due to the anharmonic interactions when the hydrogen bond is formed. We find that an orbital mass of about 100 a.u. or smaller is required in order for the ion-orbital coupling to be linear in orbital mass, and the results for which can be accurately extrapolated to the adiabatic limit of zero orbital mass. We argue that this is general for hydrogen-bonded systems, suggesting that typical orbital mass values used in CPMD are too high to accurately describe vibrational dynamics in hydrogen-bonded systems. Our results also show that the usual application of a scaling factor to the CPMD frequencies to correct for the effects of orbital mass is not valid. For the dynamics of the dimer, we find that the H-Cl stretch and the N-H-Cl bend are significantly coupled, suggesting that it is important to include the latter degree of freedom in quantum dynamical calculations. Results from our calculations with deuterium-substitution show that both these degrees of freedom have significant anharmonic interactions. Our calculated frequency for the H-Cl stretch using the Becke-exchange Lee-Yang-Parr correlation functional compares reasonably well with a previous second-order Møller-Plesset calculation with anharmonic corrections, although it is low compared to the experimental value for the dimer trapped in a neon-matrix.

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“…[l] and others cited therein) and by environmental effects [2]. Recently it has been shown that the reaction proton transfer takes place in the electronically excited state of the neutral clusters formed in free jetcooled supersonic expansion [3] or isolated in low temperature rare gas matrices [4].…”

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confidence: 99%

Infrared induced conformational change in the two strong hydrogen bonded complexes 2-1 between dimethyl ether and hydrogen iodide in nitrogen matrix

Schriver¹,

Racine²,

Schrems³

et al. 1994

Spectrochimica Acta Part A: Molecular Spectroscopy

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Ahatraet-The IR spectra of the complexes between dimethylether (DME) and hydrogen iodide in nitrogen matrices were reinvestigated with careful attention to the temperature and IR radiation effects upon the higher aggregates. Irradiation using a broad band IR source was found weakly active leading to a nearly stationary population of the two (DME)r HT species. Irradiation with CO* laser lines induced a conformational interconversion of both aggregates to non-hydrogen-bonded forms. The breaking of the strong hydrogen bond was principally governed by irradiation in the range 2600-15OOcn-' corresponding to the dCHp region whereas the reverse process was observed by increasing temperature above 27 K under the annealing limit or irradiation below llOOcm-'. No accurate evidence was found for the occurrence of photochemical proton transfer between the centrosymmetrical and asymmetrical cations characterizing the two investigated complexes.THE PROTON transfer process between two interacting molecules is one of the most interesting problems in the hydrogen bonding phenomenon. It is governed both by the proton affinities of the opposing groups (Ref.[l] and others cited therein) and by environmental effects [2]. Recently it has been shown that the reaction proton transfer takes place in the electronically excited state of the neutral clusters formed in free jetcooled supersonic expansion [3] or isolated in low temperature rare gas matrices [4]. Besides, recent studies in matrices showed that a large class of hydrogen bonded systems involving HI as proton donor were IR photosensitive (Refs [5,6] and others cited therein). In this view, it could be expected that a single quantum of excitation of a (B),(HI), cluster vibrational mode could induce proton motion by a structural change in a part of the cluster as was recognized by the end of the 1970s [7,8]. In this paper, we explore this idea showing the effects of monochromatic CO* laser or broad band (globar) irradiation on the two strong hydrogen bonded 2-l complexes involving dimethylether (DME) and hydrogen iodide, previously identified in nitrogen matrices as ion pairs (DME)*H+I- [9]. The first one, IR photosensitive, was characterized by a centrosymmetrical potential function for the proton, whereas the second one showed a proton potential function probably of the symmetrical double minimum type. The one-to-one complex was not accurately identified but it was not surprising as since that time it has been observed that complexes of HI with weak to medium strength bases quickly dissociate in the beam of the spectrometer at low temperature [6]. Also we briefly reinvestigated the DME-HI system trapped in nitrogen, and then we give results on the irradiation of the two cations (DME)*H+I-.

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Spectroscopic evidence for proton transfer within the bimolecular complex hydrogen iodide-ammonia trapped in cryogenic matrixes

Cited by 29 publications

References 4 publications

Infrared matrix isolation studies of complexes between N,N-dimethylacetamide and hydrogen halides. Part 1.—Hydrogen chloride and hydrogen bromide complexes

Infrared matrix isolation studies of complexes between N,N-dimethylacetamide and hydrogen halides. Part 1.—Hydrogen chloride and hydrogen bromide complexes

Ion-orbital coupling in Car-Parrinello calculations of hydrogen-bond vibrational dynamics: Case study with the NH3–HCl dimer

Infrared induced conformational change in the two strong hydrogen bonded complexes 2-1 between dimethyl ether and hydrogen iodide in nitrogen matrix

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