Ab initio electron correlated studies on the intracluster reaction of NO<sup>+</sup>(H2O)n → H3O<sup>+</sup>(H2O)n−2 (HONO) (n = 4 and 5)

Asada, Toshio; Nagaoka, Masataka; Koseki, Shiro

doi:10.1039/c0cp01077d

Cited by 14 publications

(25 citation statements)

References 18 publications

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“…(H 2 O) 5 with additional structures included in the electronic supplementary material. The lowest energy structure has the water molecules on one side of NO + in agreement with previous work [22]. The computed IR spectrum for this isomer is in good agreement with experiment in the high-frequency region.…”

Section: Density Functional Theory and Mp2 Studies Of No + H 2 O Andsupporting

confidence: 89%

“…Isomer 4A is similar to 3A with the additional water molecule bonding to NO + , while in 4C all of the water molecules are on the same side of NO + . The isomer 4A was also identified as the lowest energy isomer in the work of Asada et al [22]. A significant change for n = 4 is that the lowest energy isomer with HONO is only 5-8 kJ mol −1 higher in energy.…”

Section: Density Functional Theory and Mp2 Studies Of No + H 2 O Andmentioning

confidence: 83%

“…The structure and vibrational frequencies of NO + . (H 2 O) n clusters for n in the range 2-5 have been studied by several groups at the MP2, MP4 or coupled cluster levels of theory [19][20][21][22]. For the n = 2 cluster, MP2 calculations predict that the lowest energy structure has both water molecules bonding to NO + .…”

Section: Introductionmentioning

confidence: 99%

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Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Linton¹,

Wright²,

Besley³

2018

Phil. Trans. R. Soc. A.

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Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO(HO) clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO(HO) that is too high and incorrectly predict the lowest energy structure of NO(HO), and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO Ab initio molecular dynamics (AIMD) simulations were performed to study the NO(HO) [Formula: see text] H(HO) + HONO reaction to investigate the formation of HONO from NO(HO) Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO(HO) complex following its formation.This article is part of the theme issue 'Modern theoretical chemistry'.

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Section: Density Functional Theory and Mp2 Studies Of No + H 2 O Andsupporting

confidence: 89%

Section: Density Functional Theory and Mp2 Studies Of No + H 2 O Andmentioning

confidence: 83%

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Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Linton¹,

Wright²,

Besley³

2018

Phil. Trans. R. Soc. A.

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“…For the trihydrate cluster, the three experimentally detected low-lying isomers (18) are called 3-α, 3-β, and 3-γ (Fig. 1).…”

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confidence: 99%

Resolving the HONO formation mechanism in the ionosphere via ab initio molecular dynamic simulations

Zhong

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

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Solar emission produces copious nitrosonium ions (NO + ) in the D layer of the ionosphere, 60 to 90 km above the Earth's surface. NO + is believed to transfer its charge to water clusters in that region, leading to the formation of gaseous nitrous acid (HONO) and protonated water cluster. The dynamics of this reaction at the ionospheric temperature (200-220 K) and the associated mechanistic details are largely unknown. Using ab initio molecular dynamics (AIMD) simulations and transition-state search, key structures of the water hydrates-tetrahydrate NO + (H 2 O) 4 and pentahydrate NO + (H 2 O) 5 -are identified and shown to be responsible for HONO formation in the ionosphere. The critical tetrahydrate NO + (H 2 O) 4 exhibits a chainlike structure through which all of the lowest-energy isomers must go. However, most lowest-energy isomers of pentahydrate NO + (H 2 O) 5 can be converted to the HONO-containing product, encountering very low barriers, via a chain-like or a three-armed, star-like structure. Although these structures are not the global minima, at 220 K, most lowest-energy NO + (H 2 O) 4 and NO + (H 2 O) 5 isomers tend to channel through these highly populated isomers toward HONO formation.ionosphere | HONO | mechanism | water | clusters T he ionosphere is the largest layer in the Earth's atmosphere, ranging in altitude from ∼60 to 1,000 km and includes the thermosphere and parts of the mesosphere and exosphere. The ionosphere contains a high concentration of electrons and ions because of the ionization of gases in that region by short wavelength radiation from the Sun. Therefore, these species play an important role in atmospheric electricity, influencing radio propagation to different regions on the Earth's surface and space-based navigational systems (1). The D layer is the innermost layer of the ionosphere, ranging from 60 to 90 km in altitude, where Lyman series-α hydrogen radiation from the Sun gives rise to abundant nitrosonium ions (NO + ). In addition to the ionospheric reaction between NO + and water, explorations of the chemical reactivity of NO + and water clusters (2-4) have implications for understanding the mechanisms of atmospherically relevant reactions in water clusters (5-9).Over the past two decades, several experimental and theoretical studies (10-13) have focused on understanding the chemical and physical properties of the small-sized hydrated nitrosonium ion NO + (H 2 O) n , where n = 1-5. Two key processes have been proposed for HONO formation: NO + ðH 2 OÞ n + H 2 O → fðHONOÞH + ðH 2 OÞ n É → H + ðH 2 OÞ n + HONO .[1]Lee and coworkers (14) used vibrational spectroscopy to obtain clear evidence of the rearrangement of the NO + (H 2 O) n cluster by observing the appearance of new hydrogen (H)-bonded OH stretching lines. Using quantum molecular dynamics, Ye and Cheng (15) suggested possible structures and corresponding IR spectra for NO + (H 2 O) n (n = 1-3) clusters. In a major experimental breakthrough, Relph et al. (16) showed that the extent to which reaction 1 produces HONO ...

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“…(H 2 O) n and their IR spectra have been discussed in detail in previous studies. 6,26,27,32 It has been established that the lowest energy structures do not conform to structures where a rearrangement to form protonated water clusters and HONO has occurred. The lowest energy structures with HONO have been estimated to be 7.5 kJ 2600 2800 3000 3200 3400 3600 3800…”

Section: Computational Detailsmentioning

confidence: 99%

Reactivity of the O₂⁺·(H₂O)_n and NO⁺·(H₂O)_n cluster ions in the D-region of the ionosphere

Sharma

Wright

Besley

2018

Phys. Chem. Chem. Phys.

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Ab initio electron correlated studies on the intracluster reaction of NO⁺(H2O)n → H3O⁺(H2O)n−2 (HONO) (n = 4 and 5)

Cited by 14 publications

References 18 publications

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Resolving the HONO formation mechanism in the ionosphere via ab initio molecular dynamic simulations

Reactivity of the O₂⁺·(H₂O)_n and NO⁺·(H₂O)_n cluster ions in the D-region of the ionosphere

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Ab initio electron correlated studies on the intracluster reaction of NO+(H2O)n → H3O+(H2O)n−2 (HONO) (n = 4 and 5)

Cited by 14 publications

References 18 publications

Quantum chemical study of the structure, spectroscopy and reactivity of NO + .(H 2 O) n =1−5 clusters

Quantum chemical study of the structure, spectroscopy and reactivity of NO + .(H 2 O) n =1−5 clusters

Resolving the HONO formation mechanism in the ionosphere via ab initio molecular dynamic simulations

Reactivity of the O2+·(H2O)n and NO+·(H2O)n cluster ions in the D-region of the ionosphere

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Ab initio electron correlated studies on the intracluster reaction of NO⁺(H2O)n → H3O⁺(H2O)n−2 (HONO) (n = 4 and 5)

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Reactivity of the O₂⁺·(H₂O)_n and NO⁺·(H₂O)_n cluster ions in the D-region of the ionosphere