Solvation Structure and Dynamics of Ni<sup>2+</sup>(aq) from First Principles

Mareš, Jiřı́ J.; Liimatainen, Helmi; Laasonen, Kari; Vaara, Juha

doi:10.1021/ct200320z

Cited by 13 publications

(17 citation statements)

References 78 publications

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“…All the BOMD trajectories are generated in the constant volume and constant temperature (NVT) ensemble, with the Nose–Hoover chain method for controlling the temperature of the system. The integration step is set as 1 fs, which has been proven to achieve sufficient energy conservation for the water systems . The total simulation times are 147 and 200 ps, respectively, assuring that the NH 2 can reach their equilibrium positions.…”

Section: Computation Methodsmentioning

confidence: 99%

Interaction of the NH₂ Radical with the Surface of a Water Droplet

Zhong

Zhao

et al. 2015

J. Am. Chem. Soc.

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We present a comprehensive computational study of NH2 (radical) solvation in a water nanodroplet. The ab initio Born-Oppenheimer molecular dynamics simulation shows that NH2 tends to accumulate at the air-water interface. The hydrogen-bonding analysis shows that compared to the hydrogen bond of HNH··OH2, the hydrogen bond of HOH··NH2 is the dominant interaction between NH2 and water. Due to the loose hydrogen-bonding network formed between NH2 and the droplet interface, the NH2 can easily move around on the droplet surface, which speeds up the dynamics of NH2 at the air-water interface. Moreover, the structural analysis indicates that the NH2 prefers an orientation such that both N atom and one of its H atoms interact with the water droplet, while the other H atom is mostly exposed to the air. As a result, the NH2 radical becomes more accessible for reaction at the water interface. More importantly, the solvation of NH2 modifies the amplitude of vibration of the N-H bond, thereby affecting the Mulliken charges and electrophilicity of NH2. As such, reactive properties of the NH2 are altered by the droplet interface, and this can either speed up reactions or allow other reactions processes to occur in the atmosphere. Hence, the solvation of NH2 on water droplets, in chemistry of the atmosphere, may not be negligible when considering the effects of clouds.

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Section: Computation Methodsmentioning

confidence: 99%

Interaction of the NH₂ Radical with the Surface of a Water Droplet

Zhong

Zhao

et al. 2015

J. Am. Chem. Soc.

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“…The BLYP , exchange-correlation functional is used together with Grimme dispersion correction (D3) . We select the BLYP-D3 functional because it can properly describe systems with weak hydrogen-bonding interactions. − A previous AIMD simulation study using BLYP-D3 also showed good agreement between the theoretical and experimental results of the electronic absorption spectrum of liquid water . In addition to the BLYP-D3 functional, the Perdew–Burke–Ernzerhof (PBE) exchange-correlation functional with Grimme dispersion correction (D3) is also considered for geometric optimization.…”

Section: Computational Methodsmentioning

confidence: 99%

Spontaneous Formation of One-Dimensional Hydrogen Gas Hydrate in Carbon Nanotubes

et al. 2014

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We present molecular dynamics simulation evidence of spontaneous formation of quasi-one-dimensional (Q1D) hydrogen gas hydrates within single-walled carbon nanotubes (SW-CNTs) of nanometer-sized diameter (1−1.3 nm) near ambient temperature. Contrary to conventional 3D gas hydrates in which the guest molecules are typically contained in individual and isolated cages in the host lattice, the guest H 2 molecules in the Q1D gas hydrates are contained within a 1D nanochannel in which the H 2 molecules form a molecule wire. In particular, we show that in the (15,0) zigzag SW-CNT, the hexagonal H 2 hydrate tends to form, with one H 2 molecule per hexagonal prism, while in the (16,0) zigzag SW-CNT, the heptagonal H 2 hydrate tends to form, with one H 2 molecule per heptagonal prism. In contrast, in the (17,0) zigzag SW-CNT, the octagonal H 2 hydrate can form, with either one H 2 or two H 2 molecules per pentagonal prism (single or double occupancy). Interestingly, in the hexagonal or heptagonal ice nanotube, the H 2 wire is solid-like as the axial diffusion constant is very low (<5 × 10 −10 cm 2 /s), whereas in the octagonal ice nanotube, the H 2 wire is liquid-like as its axial diffusion constant is comparable to 10 −5 cm 2 /s.

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“…44 Among the DFT work, we wish to mention in particular the paper by Mareš et al 45 who presented calculations of magnetic properties, including ZFS, for aqueous nickel(II) solutions. They combined the first-principles molecular dynamics for generating hydrated ion structures 46 with DFT calculations of the ZFS, in a similar way as in earlier work from our laboratory 15 but using the state-of-the-art methods of today.…”

Section: Introductionmentioning

confidence: 99%

Zero-field splitting in nickel(II) complexes: A comparison of DFT and multi-configurational wavefunction calculations

Kubica

Kowalewski

Kruk

et al. 2013

The Journal of Chemical Physics

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A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu The Journal of Chemical Physics 132, 154104 (2010) The zero-field splitting (ZFS) is an important quantity in the electron spin Hamiltonian for S = 1 or higher. We report calculations of the ZFS in some six-and five-coordinated nickel(II) complexes (S = 1), using different levels of theory within the framework of the ORCA program package [F. Neese, Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2, 73 (2012)]. We compare the high-end ab initio calculations (complete active space self-consistent field and n-electron valence state perturbation theory), making use of both the second-order perturbation theory and the quasi-degenerate perturbation approach, with density functional theory (DFT) methods using different functionals. The pattern of results obtained at the ab initio levels is quite consistent and in reasonable agreement with experimental data. The DFT methods used to calculate the ZFS give very strongly functional-dependent results and do not seem to function well for our systems.

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Solvation Structure and Dynamics of Ni²⁺(aq) from First Principles

Cited by 13 publications

References 78 publications

Interaction of the NH₂ Radical with the Surface of a Water Droplet

Interaction of the NH₂ Radical with the Surface of a Water Droplet

Spontaneous Formation of One-Dimensional Hydrogen Gas Hydrate in Carbon Nanotubes

Zero-field splitting in nickel(II) complexes: A comparison of DFT and multi-configurational wavefunction calculations

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Solvation Structure and Dynamics of Ni2+(aq) from First Principles

Cited by 13 publications

References 78 publications

Interaction of the NH2 Radical with the Surface of a Water Droplet

Interaction of the NH2 Radical with the Surface of a Water Droplet

Spontaneous Formation of One-Dimensional Hydrogen Gas Hydrate in Carbon Nanotubes

Zero-field splitting in nickel(II) complexes: A comparison of DFT and multi-configurational wavefunction calculations

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Solvation Structure and Dynamics of Ni²⁺(aq) from First Principles

Interaction of the NH₂ Radical with the Surface of a Water Droplet

Interaction of the NH₂ Radical with the Surface of a Water Droplet