Stability of the Gaseous Ammonium Chloride Molecule

Goldfinger, Paul; Verhaegen, Georges

doi:10.1063/1.1671212

Cited by 62 publications

(42 citation statements)

References 23 publications

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“…16,[31][32][33][34][35][36] Table II gives selected bond distances, bond angles, dipole moments, rotational constants, and binding energies for the clusters, along with available experimental values. 10,37,38 It is clear from Table I that the calculated monomer properties agree well with experimental values, with deviations of less than 0.01 Å for bond lengths and 0.5°for bond angles. The calculated dipole moments are overestimated by nearly 10%, which is typical of the levels of theory and basis sets used in this study.…”

Section: Resultssupporting

confidence: 70%

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Formation of ammonium halide particles from pure ammonia and hydrogen halide gases: A theoretical study on small molecular clusters (NH3–HX)n (n=1, 2, 4; X=F, Cl, Br)

Cherng

Fang

2001

The Journal of Chemical Physics

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Articles you may be interested inModeling the hydration of mono-atomic anions from the gas phase to the bulk phase: The case of the halide ions F−, Cl−, and Br− J. Chem. Phys. 136, 044509 (2012); 10.1063/1.3678294Hydrogen-bond interaction in 1:1 complexes of tetrahydrofuran with water, hydrogen fluoride, and ammonia: A theoretical studyThe mechanism for the gas-phase production of particulate ammonium halides is studied by density functional theory and ab initio calculations on the molecular clusters of ammonia-hydrogen halide, ͑NH 3 -HX) n , nϭ1, 2, 4; XϭF, Cl, Br. The equilibrium structures of the clusters demonstrate an abrupt transition from hydrogen-bonding in the single unit of NH 3 -HX to the NH 4 ϩ¯XϪ ion-pair interactions in ͑NH 3 -HX) 4 resulting from spontaneous proton transfer from hydrogen halide to ammonia. The onset of the ion-pair form is at nϭ2 for HCl and HBr and at nϭ4 for HF. The ion-pair structure is the stable form of the larger clusters to maximize favorable electrostatic interactions and to closely resemble the crystal structures of ammonium halides. The calculated vibrational frequencies of the clusters provide additional evidence in support of the transition from hydrogen-bonding to ion-pair interactions as cluster size increases. The study shows that it is possible to form particulate ammonium halides directly from pure NH 3 and HX vapors in the homogeneous gas phase.

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Section: Resultssupporting

confidence: 70%

“…10,38 For a given cluster, the binding energy is defined relative to the isolated NH 3 and HX molecules in the cluster. ZPE corrections are based on the calculated harmonic frequencies.…”

Section: Binding Energiesmentioning

confidence: 99%

Formation of ammonium halide particles from pure ammonia and hydrogen halide gases: A theoretical study on small molecular clusters (NH3–HX)n (n=1, 2, 4; X=F, Cl, Br)

Cherng

Fang

2001

The Journal of Chemical Physics

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“…Whereas all computational results previously mentioned agree in predicting the rather shallow minimum for the NH,C1 complex as given in Figure 6, in substantial agreement with laboratory experiments [3,41, the quantitative determination of the complex binding energy deserves more attention. Note that the experimental error bracket is rather large, about 25% of the total; the complex -essentially an H-bonded system-is relatively weak, the binding energy is a few kilocalories per mole; the system is not trivially small; all these factors contribute to demand a rather accurate computation.…”

Section: Binding Energy and Geometry For The Nhcl Complexsupporting

confidence: 51%

“…In 1968, Verhaegen and Goldfinger obtained the first experimental evidence of complex formation from mass spectroscopic studies [3] and proposed a Do value between -7 / -13 kcal/mol compared with the value of -9.5,' -14 kcal/mol derived by Clementi [23 from the computed D, and zero-point energy estimates. Analyzing the infrared (IR) spectra obtained at 15 K in an N, matrix, Pimentel confirmed the H-bonded nature of the complex and estimated a value for Do in the range of -10/ -20 kcal/mol[41.…”

Section: Introductionmentioning

confidence: 98%

Revisiting the potential energy surface for [H3N �� HCl]: An ab initio and density functional theory investigation

Corongiu

Estrı́n

Murgia

et al. 1996

Int. J. Quantum Chem.

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Theoretical calculations of the potential energy surface (PES) for the [NH, + HCl] system are presented using several standard ab initio methods such as Hartree-Fock (HF), second-order Mdller-Plesset perturbation theory (MP2), coupled cluster (CC), complete active space self-consistent-field (CASSCF), density functional theory (DFT), and less traditional ab initio approaches such as Dirac-Fock four-components and the use of effective Hamiltonian techniques, such as the recently proposed K functional. All calculations predict a single minimum for the complex, corresponding to a hydrogenbonded structure, confirming early studies. The dynamical and nondynamical contributions to the correlation energy are discussed for different cuts of the PES, involving different N-Cl distances. The complex has also been characterized by performing a full geometry optimization within the HF and DFT schemes; with the latter we have performed also the vibrational analysis. The predicted binding energies and infrared (IR) spectrum are compared with other theoretical and experimental results. For the gas phase, we propose a binding energy of -5.3 f 0.5 kcal/mol, thus revising the experimental value of -8.0 k 2.8 kcal/mol; for the minimum, the predicted N-H and * is done with approximate inclusion of solvent effects (Onsager reaction field), the minimum is shifted and it corresponds to the ion pair NH:. C1-structure, similar to Mulliken's outer complex. Since the first ab initio computation for the NH,Cl complex is the pioneer work in 1967 by E. Clementi, the present work provides us with an opportunity to comment on some aspects of the evolution in computational chemistry, particularly for energy determinations. We have concluded our comments with the invitation to use four-components Fock-Dirac for molecules both with high and low Z atoms, rather than the traditional Hartree-Fock and related methods. In other words, we are of the opinion that the time is ready in quantum chemistry to switch from the Schrodinger to the Dirac representation, due to new developments in computer hardware and software. In addition, the use of effective Hamiltonians, like the recently proposed " K functional," seems to deserve attention, because of their computational simplicity and physical reliability in predicting correlation corrections. 0 1996 John Wiley & Sons, Inc.

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“…This commonly held view was challenged by ab initio calculation of the electronic structure of the NH4CI molecule predicting a minimum in the NH4CI potential energy surface that would be 19kcalmol -1 lower than the energy of its dissociation products [157]. Shortly thereafter, Golfinger and Verhagen [158] using quadrupole mass spectroscopy provided unambiguous evidence for the presence of undissociated deuterated ammonium chloride in the vapor effusing from a Knudsen cell. Shibata [159] further demonstrated the presence of undissociated ammonium chloride in the gas phase, using electron diffraction spectroscopy.…”

Section: Gas-phase Reaction Of Ammonia and Hydrochloric Acidmentioning

confidence: 99%

Fate of ammonia in the atmosphere?a review for applicability to hazardous releases

Renard

Calidonna

Henley³

2004

Journal of Hazardous Materials

138

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Stability of the Gaseous Ammonium Chloride Molecule

Cited by 62 publications

References 23 publications

Formation of ammonium halide particles from pure ammonia and hydrogen halide gases: A theoretical study on small molecular clusters (NH3–HX)n (n=1, 2, 4; X=F, Cl, Br)

Formation of ammonium halide particles from pure ammonia and hydrogen halide gases: A theoretical study on small molecular clusters (NH3–HX)n (n=1, 2, 4; X=F, Cl, Br)

Revisiting the potential energy surface for [H3N �� HCl]: An ab initio and density functional theory investigation

Fate of ammonia in the atmosphere?a review for applicability to hazardous releases

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Stability of the Gaseous Ammonium Chloride Molecule

Cited by 62 publications

References 23 publications

Formation of ammonium halide particles from pure ammonia and hydrogen halide gases: A theoretical study on small molecular clusters (NH3–HX)n (n=1, 2, 4; X=F, Cl, Br)

Formation of ammonium halide particles from pure ammonia and hydrogen halide gases: A theoretical study on small molecular clusters (NH3–HX)n (n=1, 2, 4; X=F, Cl, Br)

Revisiting the potential energy surface for [H3N ��� HCl]: An ab initio and density functional theory investigation

Fate of ammonia in the atmosphere?a review for applicability to hazardous releases

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Product

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Revisiting the potential energy surface for [H3N �� HCl]: An ab initio and density functional theory investigation