Intramolecular Reactions in Ionized Ammonia Clusters: A Direct Ab Initio Molecular Dynamics Study

Tachikawa, Hiroto

doi:10.1021/acs.jpca.9b11122

Cited by 13 publications

(9 citation statements)

References 41 publications

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“…A similar tendency is obtained at the PBE0-D3/6-311++g(2df,2pd), B3LYP-D3/6-311++g(2df,2pd), MP2/aug-cc-pvdz, MP2/aug-cc-pvtz, and MP2/6-31++g(d,p) levels, as shown in Table S1 in the Supporting Information. These geometric structure parameters of MP2 with basis set investigations are in good agreement with DFT. ,− The trend is consistent with the previous view that bond lengths decrease gradually with the increase of the number of n . ,− Moreover, we present the average O–H bond lengths as well as the average ∠H···NH bond angles in Figure . As the n value increases, the N–H bond lengths and ∠H···NH bond angles increase, leading to a decrease of N···H bond lengths.…”

Section: Resultssupporting

confidence: 90%

Understanding the Hydrogen-Bonded Clusters of Ammonia (NH₃)_n (n = 3–6): Insights from the Electronic Structure Theory

et al. 2020

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Although it is well known that hydrogen bonds commonly exist in ammonia clusters and play an important role, there are still many challenges in understanding the electronic structure properties of hydrogen bonds. In this paper, the geometric and electronic structure properties of cyclic ammonia clusters are investigated by using first-principles density functional theory (DFT) and the Møller−Plesset perturbation theory (MP2). The calculation results show that the pentamer and hexamer have deviated from the perfect plane, while the trimer and tetramer present planarization that has been confirmed by infrared (IR) spectra. The electronic structure analysis further shows that the covalent properties play a non-negligible role in hydrogen bonding. The results also indicate that the electronic structure facilitates structure planarization. Our work not only provides insight into the role and nature of hydrogen bonds in ammonia clusters but also provides a theoretical basis for frontier science in fields such as atmospheric haze and biomolecular functions.

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Section: Resultssupporting

confidence: 90%

Understanding the Hydrogen-Bonded Clusters of Ammonia (NH₃)_n (n = 3–6): Insights from the Electronic Structure Theory

et al. 2020

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“…On the other hand, in the case of or the [PhOH-(NH3)2-6] + cluster cations, proton transfer is spontaneous even in the presence of two ammonia molecules. 28 Further, the BOMD trajectories were also calculated for several PhOH-(NH3)5-10 clusters (starting from 5A, 5C, 6A, 6B, 6E, 7A, 7B, 7C, 8A, 8B, 8C, 9B, 10C, 10E, and 10F geometries, from Ref. 16).…”

Section: (B) Proton Transfer In Bomd Simulationsmentioning

confidence: 99%

Ultrafast Proton Transfer Reaction in Phenol–(Ammonia)n Clusters: An Ab-Initio Molecular Dynamics Investigation.

Pant

Singh

Patwari

2021

Preprint

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The ability of phenol to transfer the proton to surrounding ammonia molecules in a phenol-(ammonia)n cluster will depend on the relative orientation of the ammonia molecules and a critical field of about 285 MV cm-1 is essential along the O–H bond for the transfer process. Ab-initio MD simulations reveal that for a spontaneous proton transfer process, the phenol molecule must be embedded in a cluster consisting of at least eight ammonia molecules, even though several local minima with proton transferred can be observed for clusters consisting of 5-7 ammonia molecules. Further, phenol solvated in large clusters of ammonia, the proton transfer is spontaneous with the proton transfer event being instantaneous (about 20-120 fs). These simulations indicate that the rate-determining step for the proton transfer process is the organization of the solvent around the OH group and the proton transfer process in phenol-(ammonia)n clusters follows a curvilinear path which includes the O–H bond elongation and out-of-plane movement of the proton and can be referred to as a “Bend-to-Break” process.

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“…In the present study, the intracluster reactions of O(X)(H 2 O) n (X = 3 P, 1 D, and 1 S, and n = 1–6), following the photoelectron detachment of a water cluster of an oxygen radical anion (O – (H 2 O) n , n = 1–6), were investigated using the direct ab initio molecular dynamics (AIMD) method. − Three low-lying electronic states of oxygen atoms, O( 3 P), O( 1 D), and O( 1 S), were examined. We found that the O( 1 S)(H 2 O) n complexes spontaneously convert into H 2 O 2 after electron detachment.…”

Section: Introductionmentioning

confidence: 99%

Formation of Hydrogen Peroxide from O^–(H₂O)_n Clusters

Tachikawa

2021

J. Phys. Chem. A

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Hydrogen peroxide (H2O2) has recently received much attention as a safe and clean energy carrier for hydrogen molecules. In this study, based on direct ab initio molecular dynamics (AIMD) calculations, we demonstrated that H2O2 is directly formed via the photoelectron detachment of O–(H2O) n (n = 1–6) (water clusters of an oxygen radical anion). Three electronic states of oxygen atoms were examined in the calculations: O(X)(H2O) n (X = 3P, 1D, and 1S states). After the photoelectron detachment of O–(H2O) n (n = 1) to the 1S state, a complex comprising O(1S) and H2O, O(1 S)-OH2, was formed. A hydrogen atom of H2O immediately transferred to O(1S) during an intracluster reaction to form H2O2 as the final product. Simulations were run to obtain a total of 33 trajectories for n = 1 that all led to the formation of H2O2. The average reaction time of H2O2 formation was calculated to be 57.7 fs in the case of n = 1, indicating that the reaction was completed within 100 fs of electron detachment. All the reaction systems O(1S)(H2O) n (n = 1–6) indicated the formation of H2O2 by the same mechanism. The reaction times for n = 2–6 were calculated to range between 80 and 180 fs, indicating that the reaction for n = 1 is faster than that of the larger clusters, that is, the larger the cluster size, the slower the reaction is. The reaction dynamics of the triplet O(3P) and singlet O(1D) potential energy surfaces were calculated for comparison. All calculations yielded the dissociation product O(X)(H2O) n → O(X) + (H2O) n (X = 3P and 1D), indicating that the O(1S) state contributes to the formation of H2O2. The reaction mechanism was discussed based on the theoretical results.

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Intramolecular Reactions in Ionized Ammonia Clusters: A Direct Ab Initio Molecular Dynamics Study

Cited by 13 publications

References 41 publications

Understanding the Hydrogen-Bonded Clusters of Ammonia (NH₃)_n (n = 3–6): Insights from the Electronic Structure Theory

Understanding the Hydrogen-Bonded Clusters of Ammonia (NH₃)_n (n = 3–6): Insights from the Electronic Structure Theory

Ultrafast Proton Transfer Reaction in Phenol–(Ammonia)n Clusters: An Ab-Initio Molecular Dynamics Investigation.

Formation of Hydrogen Peroxide from O^–(H₂O)_n Clusters

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Intramolecular Reactions in Ionized Ammonia Clusters: A Direct Ab Initio Molecular Dynamics Study

Cited by 13 publications

References 41 publications

Understanding the Hydrogen-Bonded Clusters of Ammonia (NH3)n (n = 3–6): Insights from the Electronic Structure Theory

Understanding the Hydrogen-Bonded Clusters of Ammonia (NH3)n (n = 3–6): Insights from the Electronic Structure Theory

Ultrafast Proton Transfer Reaction in Phenol–(Ammonia)n Clusters: An Ab-Initio Molecular Dynamics Investigation.

Formation of Hydrogen Peroxide from O–(H2O)n Clusters

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Understanding the Hydrogen-Bonded Clusters of Ammonia (NH₃)_n (n = 3–6): Insights from the Electronic Structure Theory

Understanding the Hydrogen-Bonded Clusters of Ammonia (NH₃)_n (n = 3–6): Insights from the Electronic Structure Theory

Formation of Hydrogen Peroxide from O^–(H₂O)_n Clusters