Car–Parrinello Molecular Dynamics Study of DCl Hydrate Crystals

Sillanpää, Atte; Laasonen, Kari

doi:10.1002/cphc.200400588

Cited by 11 publications

(10 citation statements)

References 26 publications

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“…The low-energy minima structures of HCl(H 2 O) n clusters with n ≤ 6 have been explored using different electronic structure methods. − In the past decade, both Car–Parrinello (CPMD) and Born–Oppenheimer (BOMD) molecular dynamics simulations were carried for HCl(H 2 O) n clusters with n ≤ 6 and their deuterated analogs. ,,,− These ab initio molecular dynamics (AIMD) simulations show that the relative stability of different HCl(H 2 O) 6 isomers is significantly affected by temperature . CPMD simulations carried out for DCl(D 2 O) n with n = 1–6 were also used to determine the relationships between energies, structures, and spectroscopic features .…”

Section: Introductionmentioning

confidence: 99%

Systematic Study of Structural and Thermodynamic Properties of HCl(H₂O)_n Clusters from Semiempirical Replica Exchange Simulations

Lin

Paesani

2013

J. Phys. Chem. A

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The structural and thermodynamic properties of HCl(H2O)n clusters with n = 4-10 are studied using Born-Oppenheimer replica exchange molecular dynamics simulations with the PM3-MAIS semiempirical Hamiltonian. Independently of the cluster size, the simulations predict that HCl exists in the dissociated form in all low-energy isomers. Different local structures are identified within the clusters due to the presence of the dissociated proton, including Zundel, Eigen, Eigen-like, H7O3(+), and intermediate Zundel-Eigen configurations. As the cluster size increases, several groups of isomers are identified, whose relative stabilities vary as a function of temperature. A detailed analysis of the heat capacity indicates that the melting behavior of HCl(H2O)n clusters is strongly size-dependent. In particular, melting is observed in clusters with n = 7-10 in the temperature range T = 100-150 K. By contrast, melting is not observed in clusters with n = 4-6. Minimum energy structures for HCl(H2O)n clusters with n = 11-15 and n = 21 are also characterized.

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Section: Introductionmentioning

confidence: 99%

Systematic Study of Structural and Thermodynamic Properties of HCl(H₂O)_n Clusters from Semiempirical Replica Exchange Simulations

Lin

Paesani

2013

J. Phys. Chem. A

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“…Past computational studies of the HCl hydrate systems included modeling of the monohydrate, dihydrate, and trihydrate using Car−Parrinello molecular dynamics (CPMD) and Car−Parrinello path integral molecular dynamics CP-PIMD and another more recent CPMD study of these systems …”

Section: Introductionmentioning

confidence: 99%

HCl Hydrates as Model Systems for Protonated Water

Buch¹,

Dubrovskiy²,

Mohamed³

et al. 2008

J. Phys. Chem. A

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Ab initio molecular dynamics simulations are presented of vibrational dynamics and spectra of crystal HCl hydrates. Depending on the composition, the hydrates include distinct protonated water forms, which in their equilibrium structures approximate either the Eigen ion H3O+(H2O)3 (in the hexahydrate) or the Zundel H2O...H+...OH2 ion (in the di- and trihydrate). Thus, the hydrates offer the opportunity to study spectra and dynamics of distinct species of protonated water trapped in a semirigid solvating environment. The experimentally measured spectra are reproduced quite well by BLYP/DZVP-level calculations employing Fourier transform of the system dipole. The large overall width (800-1000 cm-1) of structured proton bands reflects a broad range of solvating environments generated by crystal vibrations. The aqueous HCl solution was also examined in search of an objective criterion for separating the contributions of "Zundel-like" and "Eigen-like" protonated forms. It is suggested that no such criterion exists since distributions of proton-related structural properties appear continuous and unimodal. Dipole derivatives with respect to OH and O...H+ stretches in water and protonated water were also investigated to advance the understanding of the corresponding IR intensities. The effects of H bonding and solvation on the intensities were analyzed with the help of the Wannier centers' representation of electron density.

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“…We use the HCl–water cluster system to illustrate and validate the present first-order quantum vibration perturbation (QVP1) approach because strong hydrogen-bonding and dispersion interactions are important and because it has been extensively investigated experimentally − and theoretically. − Although this appears to be a small test case, it is in fact challenging because of the strong bond-dissociation character in the oscillator mode. We emphasize that the QVP1 method is equally efficient for condensed-phase simulations as in a combined QM/MM approach .…”

Section: Introductionmentioning

confidence: 99%

“…Recently, Havenith and co-workers confirmed that the broad band at 2675 cm –1 is due to the dissociated cluster, H 3 O + (H 2 O) 3 Cl – . On the theoretical side, Born–Oppenheimer molecular dynamics (BOMD) simulations with DFT-based potentials have been used to mode HCl(H 2 O) n ( n = 1–4) clusters. ,− ,, Marx and co-workers obtained the IR spectra of the HCl–water clusters using the BLYP density functional. A sequential solvation process was proposed to account for the HCl dissociation mechanism, involving the interplay of quantum tunneling and thermal fluctuations from path integral simulations. ,,− Employing a semiempirical PM3-MAIS potential, Lin and Paesani extended the investigation to larger clusters up to n = 21 .…”

Section: Introductionmentioning

confidence: 99%

“…59 On the theoretical side, Born− Oppenheimer molecular dynamics (BOMD) simulations with DFT-based potentials have been used to mode HCl(H 2 O) n (n = 1−4) clusters. 38,[40][41][42][43][44][45]47,60 Marx and co-workers 47 obtained the IR spectra of the HCl−water clusters using the BLYP density functional. A sequential solvation process was proposed to account for the HCl dissociation mechanism, involving the interplay of quantum tunneling and thermal fluctuations from path integral simulations.…”

Section: Introductionmentioning

confidence: 99%

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Perturbation Approach for Computing Infrared Spectra of the Local Mode of Probe Molecules

Xue

Grofe

Yin

et al. 2016

J. Chem. Theory Comput.

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Linear and two-dimensional infrared (IR) spectroscopy of site-specific probe molecules provides an opportunity to gain a molecular-level understanding of the local hydrogen-bonding network, conformational dynamics, and long-range electrostatic interactions in condensed-phase and biological systems. A challenge in computation is to determine the time-dependent vibrational frequencies that incorporate explicitly both nuclear quantum effects of vibrational motions and an electronic structural representation of the potential energy surface. In this paper, a nuclear quantum vibrational perturbation (QVP) method is described for efficiently determining the instantaneous vibrational frequency of a chromophore in molecular dynamics simulations. Computational efficiency is achieved through the use of (a) discrete variable representation of the vibrational wave functions, (b) a perturbation theory to evaluate the vibrational energy shifts due to solvent dynamic fluctuations, and (c) a combined QM/MM potential for the systems. It was found that first-order perturbation is sufficiently accurate, enabling time-dependent vibrational frequencies to be obtained on the fly in molecular dynamics. The QVP method is illustrated in the mode-specific linear and 2D-IR spectra of the H–Cl stretching frequency in the HCl–water clusters and the carbonyl stretching vibration of acetone in aqueous solution. To further reduce computational cost, a hybrid strategy was proposed, and it was found that the computed vibrational spectral peak position and line shape are in agreement with experimental results. In addition, it was found that anharmonicity is significant in the H–Cl stretching mode, and hydrogen-bonding interactions further enhance anharmonic effects. The present QVP method complements other computational approaches, including path integral-based molecular dynamics, and represents a major improvement over the electrostatics-based spectroscopic mapping procedures.

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Car–Parrinello Molecular Dynamics Study of DCl Hydrate Crystals

Cited by 11 publications

References 26 publications

Systematic Study of Structural and Thermodynamic Properties of HCl(H₂O)_n Clusters from Semiempirical Replica Exchange Simulations

Systematic Study of Structural and Thermodynamic Properties of HCl(H₂O)_n Clusters from Semiempirical Replica Exchange Simulations

HCl Hydrates as Model Systems for Protonated Water

Perturbation Approach for Computing Infrared Spectra of the Local Mode of Probe Molecules

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Car–Parrinello Molecular Dynamics Study of DCl Hydrate Crystals

Cited by 11 publications

References 26 publications

Systematic Study of Structural and Thermodynamic Properties of HCl(H2O)n Clusters from Semiempirical Replica Exchange Simulations

Systematic Study of Structural and Thermodynamic Properties of HCl(H2O)n Clusters from Semiempirical Replica Exchange Simulations

HCl Hydrates as Model Systems for Protonated Water

Perturbation Approach for Computing Infrared Spectra of the Local Mode of Probe Molecules

Contact Info

Product

Resources

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Systematic Study of Structural and Thermodynamic Properties of HCl(H₂O)_n Clusters from Semiempirical Replica Exchange Simulations

Systematic Study of Structural and Thermodynamic Properties of HCl(H₂O)_n Clusters from Semiempirical Replica Exchange Simulations