Theoretical study on mechanisms of structural rearrangement and ionic dissociation in the HCl(H2O)4 cluster with path-integral molecular dynamics simulations

Sugawara, Shuichi; Yoshikawa, Takehiro; Takayanagi, Toshiyuki; Tachikawa, Masanori

doi:10.1016/j.cplett.2010.11.051

Cited by 22 publications

(42 citation statements)

References 33 publications

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“…The D 0 of the fully deuterated isotopologue is calculated to be 1476 ± 3 cm −1 , which we hope will stand as a benchmark for future experimental work. [1][2][3][4][5][6] and theoretical [7][8][9][10][11] studies. The high interest in these complexes is due to their impact on atmospheric chemistry, specifically their role in ozone depletion.…”

mentioning

confidence: 99%

Communication: A new ab initio potential energy surface for HCl–H2O, diffusion Monte Carlo calculations of D and a delocalized zero-point wavefunction

Mancini

Bowman

2013

The Journal of Chemical Physics

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confidence: 99%

Communication: A new ab initio potential energy surface for HCl–H2O, diffusion Monte Carlo calculations of D and a delocalized zero-point wavefunction

Mancini

Bowman

2013

The Journal of Chemical Physics

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“…The mean value of δ determined from the two probability distributions shown in Figure 7 is −0.1 and 0.06 Å for n = 10 and 21, respectively. These values indicate that, on average, the excess proton forms a hydronium-like structure with molecule a in HCl(H 2 O) 10 and with molecule b in HCl-(H 2 O) 21 . On the basis of this analysis and the AVPM results, the frequency assignment of the vibrational modes associated with the H 5 O 2 + core in HCl(H 2 O) 10 and HCl(H 2 O) 21 becomes straightforward.…”

Section: Results and Discusstionmentioning

confidence: 93%

“…28 Blue shifts of 500−600 cm −1 relative to the frequency (∼1170 cm −1 ) of the proton oscillation in the 4A1Z Zundel-type structure are found in all clusters containing the H 5 O 2 + (H 2 O) 3 Cl − moiety (red peaks in Figure 5). 10 and to water b in HCl(H 2 O) 21 (Figure 6c). To determine the effects of the excess proton position on the corresponding IR spectra, δ = r O a H* − r O b H* was calculated for the shared proton (H*) of the H 5 O 2 + core in HCl(H 2 O) 10 and HCl(H 2 O) 21 along the MD trajectories.…”

Section: Results and Discusstionmentioning

confidence: 98%

“…10 and to water b in HCl(H 2 O) 21 (Figure 6c). To determine the effects of the excess proton position on the corresponding IR spectra, δ = r O a H* − r O b H* was calculated for the shared proton (H*) of the H 5 O 2 + core in HCl(H 2 O) 10 and HCl(H 2 O) 21 along the MD trajectories. The mean value of δ determined from the two probability distributions shown in Figure 7 is −0.1 and 0.06 Å for n = 10 and 21, respectively.…”

Section: Results and Discusstionmentioning

confidence: 98%

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Infrared Spectra of HCl(H₂O)_n Clusters from Semiempirical Born–Oppenheimer Molecular Dynamics Simulations

Lin

Paesani

2014

J. Phys. Chem. A

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Infrared spectra of HCl(H2O)n clusters, with n = 4-10 and 21, are calculated at T = 50 K from semiempirical Born-Oppenheimer molecular dynamics simulations performed with the PM3-MAIS model. The specific focus of this study is on the relationship between spectroscopic features associated with the presence of the excess proton generated by the HCl dissociation as a function of n and the underlying water hydrogen-bonding topologies. Vibrational modes involving the motion of the excess proton are attributed to specific features appearing at ∼1175 cm(-1) for Zundel-type structures, in the 1670-1800 cm(-1) range for intermediate Zundel-Eigen-type structures, and at ∼2820 cm(-1) for Eigen-type structures. This broad range of vibrational frequencies correlates with the position of the excess proton within the clusters. Overall, the theoretical predictions are in good agreement with the available experimental data.

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“…(See, e.g., Ref. [31] as well as [32][33][34][35].) In the bulk, dissociation of an acid molecule clearly implies separation of its charged constituents.…”

Section: Introductionmentioning

confidence: 99%

Electric Dipole Moments of Nanosolvated Acid Molecules in Water Clusters

2015

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The electric dipole moments of (H 2 O) n DCl (n=3-9) clusters have been measured by the beam deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation.The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility.There is evidence for a noticeable rise in the dipole moment occurring at n≈5-6. This size is consistent with predictions for the onset of ionic dissociation. Additionally, a molecular dynamics model suggests that even with a nominally bound impurity an enhanced dipole moment can arise due to the thermal and zero point motion of the proton and the water molecules. The experimental measurements and the calculations draw attention to the importance of fluctuations in defining the polarity of water-based nanoclusters, and generally to the essential role played by motional effects in determining the response of fluxional nanoscale systems under realistic conditions. 2 INTRODUCTION.Water clusters are convenient experimental platforms for the study of the microscopic physics and chemistry of solvation. By monitoring cluster properties as a function of the number of water molecules, it is possible to follow the step-by-step progression of intermolecular interactions [1], following the transition from isolated molecule to bulk By virtue of having a large fraction of their molecules located near the surface, clusters can serve as surrogates for important processes occurring on aerosols and hydrometeors [2,3]. Composed of only a finite number of constituents, they often serve as test beds for theoretical methods and models.Small water clusters doped with an acid molecule -here, for concreteness, hydrogen chloride -have been the subject of a great number of theoretical papers and a sizeable (but regrettably much smaller) number of experimental ones. Hydrogen chloride readily dissociates into H 3 O + and Cl -and the dissociation also takes place in HCl hydrates [4][5][6][7][8], on the ice surface [9][10][11][12] or on larger water nanoparticles [13][14][15] and protonated water cluster ions [16,17]. One inquiry that persistently threads its way through this subject is: what is the minimum quantity of water molecules, (H 2 O) n , required to dissociate the acid [18]? According to calculations, the acidically dissociated structure is supported starting from n=4; most of the theoretical approaches agree that at this size the dissociated form represents the global minimum on the potential energy surface [18][19][20][21][22][23][24]. Experimentally, for neutral clusters the question has been probed by laser spectroscopy (see, e.g., [25][26][27][28]) but finding a conclusive spectroscopic signature of the onset of dissociation in a nanocluster is not straightforward.As a matter of fact, the challenge is not just experimental but conceptual. The free water clusters in natural and laboratory environments generally exist at temperatures appreciably above absolute zero ...

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Theoretical study on mechanisms of structural rearrangement and ionic dissociation in the HCl(H2O)4 cluster with path-integral molecular dynamics simulations

Cited by 22 publications

References 33 publications

Communication: A new ab initio potential energy surface for HCl–H2O, diffusion Monte Carlo calculations of D and a delocalized zero-point wavefunction

Communication: A new ab initio potential energy surface for HCl–H2O, diffusion Monte Carlo calculations of D and a delocalized zero-point wavefunction

Infrared Spectra of HCl(H₂O)_n Clusters from Semiempirical Born–Oppenheimer Molecular Dynamics Simulations

Electric Dipole Moments of Nanosolvated Acid Molecules in Water Clusters

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Theoretical study on mechanisms of structural rearrangement and ionic dissociation in the HCl(H2O)4 cluster with path-integral molecular dynamics simulations

Cited by 22 publications

References 33 publications

Communication: A new ab initio potential energy surface for HCl–H2O, diffusion Monte Carlo calculations of D and a delocalized zero-point wavefunction

Communication: A new ab initio potential energy surface for HCl–H2O, diffusion Monte Carlo calculations of D and a delocalized zero-point wavefunction

Infrared Spectra of HCl(H2O)n Clusters from Semiempirical Born–Oppenheimer Molecular Dynamics Simulations

Electric Dipole Moments of Nanosolvated Acid Molecules in Water Clusters

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Infrared Spectra of HCl(H₂O)_n Clusters from Semiempirical Born–Oppenheimer Molecular Dynamics Simulations