Ab Initio Investigations of Stable
Geometries of the Atmospheric Negative
Ion NO 3
−
(HNO 3 ) 2 and Its Monohydrate
Atsuko Ueda, Yukiumi Kita, Kanako Sekimoto
and Masanori Tachikawa
Abstract The possible stable geometries of the atmospheric negative core ion
NO
−
3 HNO 3
ð
Þ 2 and its monohydrate were theoretically investigated with the second
order Møller-Plesset perturbation theory (MP2) in consideration of the effect of
electron correlation. For both ionic clusters, we obtained the different stable
geometries from the previous study by Drenck and coworkers (Int J Mass Spectrom
273:126–131, 2008) [1] with the density functional theory of Becke 3-parameters
hybrid functional (B3LYP). The non-planar geometry with two hydrogen-bondings
between one oxygen atom on NO
−
3 and each hydrogen atom of two HNO 3 fragments is found as the most stable structure of the core ion at 0 K. For the monohydrate, the most stable geometry at 0 K is found as the H 2 O-embedded form in
which one water molecule is located at the center of the cluster with
hydrogen-bondings to NO
−
3 and HNO 3 fragments. Our results show that the
hydrogen bond network of the core ion can be strongly perturbed by a single water
molecule. We also discussed the relative abundance of conformers of these ionic
clusters under a finite temperature.
1 Introduction
Atmospheric ions are led by multistage reactions, e.g. a charge-transfer reaction, an
ion induced nucleation, etc. [2]. Atmospheric ions affect an atmospheric environment by generating atmospheric aerosols [3, 4]. Atmospheric ion clusters consisting
of organic compounds, water molecule, etc. have a crucial role in physical and
chemical processes in the atmosphere. Negative ion clusters in the atmosphere lead
to acid rain which has been known to affect the environment, e.g. forest trees,
plants, animals, and buildings [5]. Especially H 2 SO 4 and HNO 3 have the dominant
contribution to acid rain, because strong acids release H
+ when water vapor exists
A. Ueda ⋅ Y. Kita ( ✉ ) ⋅ K. Sekimoto ⋅ M. Tachikawa
Quantum Chemistry Division, Yokohama City University,
Seto 22-2, Kanazawa-ku, Yokohama 236-0027, Japan
e-mail: ykita@yokohama-cu.ac.jp
© Springer International Publishing AG, part of Springer Nature 2018
Y. A. Wang et al. (eds.), Concepts, Methods and Applications of Quantum Systems
in Chemistry and Physics, Progress in Theoretical Chemistry and Physics 31,
https://doi.org/10.1007/978-3-319-74582-4_10
193
Geometries of the Atmospheric Negative
Ion NO 3
−
(HNO 3 ) 2 and Its Monohydrate
Atsuko Ueda, Yukiumi Kita, Kanako Sekimoto
and Masanori Tachikawa
Abstract The possible stable geometries of the atmospheric negative core ion
NO
−
3 HNO 3
ð
Þ 2 and its monohydrate were theoretically investigated with the second
order Møller-Plesset perturbation theory (MP2) in consideration of the effect of
electron correlation. For both ionic clusters, we obtained the different stable
geometries from the previous study by Drenck and coworkers (Int J Mass Spectrom
273:126–131, 2008) [1] with the density functional theory of Becke 3-parameters
hybrid functional (B3LYP). The non-planar geometry with two hydrogen-bondings
between one oxygen atom on NO
−
3 and each hydrogen atom of two HNO 3 fragments is found as the most stable structure of the core ion at 0 K. For the monohydrate, the most stable geometry at 0 K is found as the H 2 O-embedded form in
which one water molecule is located at the center of the cluster with
hydrogen-bondings to NO
−
3 and HNO 3 fragments. Our results show that the
hydrogen bond network of the core ion can be strongly perturbed by a single water
molecule. We also discussed the relative abundance of conformers of these ionic
clusters under a finite temperature.
1 Introduction
Atmospheric ions are led by multistage reactions, e.g. a charge-transfer reaction, an
ion induced nucleation, etc. [2]. Atmospheric ions affect an atmospheric environment by generating atmospheric aerosols [3, 4]. Atmospheric ion clusters consisting
of organic compounds, water molecule, etc. have a crucial role in physical and
chemical processes in the atmosphere. Negative ion clusters in the atmosphere lead
to acid rain which has been known to affect the environment, e.g. forest trees,
plants, animals, and buildings [5]. Especially H 2 SO 4 and HNO 3 have the dominant
contribution to acid rain, because strong acids release H
+ when water vapor exists
A. Ueda ⋅ Y. Kita ( ✉ ) ⋅ K. Sekimoto ⋅ M. Tachikawa
Quantum Chemistry Division, Yokohama City University,
Seto 22-2, Kanazawa-ku, Yokohama 236-0027, Japan
e-mail: ykita@yokohama-cu.ac.jp
© Springer International Publishing AG, part of Springer Nature 2018
Y. A. Wang et al. (eds.), Concepts, Methods and Applications of Quantum Systems
in Chemistry and Physics, Progress in Theoretical Chemistry and Physics 31,
https://doi.org/10.1007/978-3-319-74582-4_10
193