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Title: Coexistence of neutral and ion-pair clusters of hydrated sulfuric acid H{sub 2}SO{sub 4}(H{sub 2}O){sub n} (n = 1--5) -- a molecular orbital study

Abstract

Various isomeric structures of the hydrated clusters of sulfuric acid, H{sub 2}SO{sub 4}(H{sub 2}O){sub n} (n = 1--5), are examined using a density functional molecular orbital method. Due to the small energy difference between trans and cis conformations about two OH groups of sulfuric acid, there are three types of isomeric forms of the hydrated clusters of sulfuric acid which involve the proton nontransferred trans conformer, the proton transferred trans conformer, and the proton nontransferred cis conformer of sulfuric acid. In the case of transoid H{sub 2}SO{sub 4}, the proton transferred ion-pair structures become more stable than the proton nontransferred structures as the number of water molecules increases. The hydrated clusters of the cis conformation remain neutral hydrogen-bonded structures even if the number of water molecules increases. All stable clusters tend to form multicyclic structures. While both protons of sulfuric acid participate in cyclic hydrogen bonding in the neutral structures, the OH group o HSO{sub 4}{sup {minus}} in the ion-pair structures remains dangling because the counterion H{sub 2}O{sup +} prefers to make strong hydrogen bonds with water molecules and/or the HSO{sub 4}{sup {minus}} moiety.

Authors:
;  [1];  [2]
  1. Rikkyo Univ., Tokyo (Japan). Dept. of Chemistry
  2. Emory Univ., Atlanta, GA (United States)
Publication Date:
OSTI Identifier:
355562
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 18; Other Information: PBD: 6 May 1999
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; ATMOSPHERIC CHEMISTRY; SULFURIC ACID; HYDRATION; AIR POLLUTION; CHEMICAL BONDS; MOLECULAR STRUCTURE

Citation Formats

Re, S, Osamura, Yoshihiro, Emory Univ., Atlanta, GA, and Morokuma, Keiji. Coexistence of neutral and ion-pair clusters of hydrated sulfuric acid H{sub 2}SO{sub 4}(H{sub 2}O){sub n} (n = 1--5) -- a molecular orbital study. United States: N. p., 1999. Web. doi:10.1021/jp984759x.
Re, S, Osamura, Yoshihiro, Emory Univ., Atlanta, GA, & Morokuma, Keiji. Coexistence of neutral and ion-pair clusters of hydrated sulfuric acid H{sub 2}SO{sub 4}(H{sub 2}O){sub n} (n = 1--5) -- a molecular orbital study. United States. doi:10.1021/jp984759x.
Re, S, Osamura, Yoshihiro, Emory Univ., Atlanta, GA, and Morokuma, Keiji. Thu . "Coexistence of neutral and ion-pair clusters of hydrated sulfuric acid H{sub 2}SO{sub 4}(H{sub 2}O){sub n} (n = 1--5) -- a molecular orbital study". United States. doi:10.1021/jp984759x.
@article{osti_355562,
title = {Coexistence of neutral and ion-pair clusters of hydrated sulfuric acid H{sub 2}SO{sub 4}(H{sub 2}O){sub n} (n = 1--5) -- a molecular orbital study},
author = {Re, S and Osamura, Yoshihiro and Emory Univ., Atlanta, GA and Morokuma, Keiji},
abstractNote = {Various isomeric structures of the hydrated clusters of sulfuric acid, H{sub 2}SO{sub 4}(H{sub 2}O){sub n} (n = 1--5), are examined using a density functional molecular orbital method. Due to the small energy difference between trans and cis conformations about two OH groups of sulfuric acid, there are three types of isomeric forms of the hydrated clusters of sulfuric acid which involve the proton nontransferred trans conformer, the proton transferred trans conformer, and the proton nontransferred cis conformer of sulfuric acid. In the case of transoid H{sub 2}SO{sub 4}, the proton transferred ion-pair structures become more stable than the proton nontransferred structures as the number of water molecules increases. The hydrated clusters of the cis conformation remain neutral hydrogen-bonded structures even if the number of water molecules increases. All stable clusters tend to form multicyclic structures. While both protons of sulfuric acid participate in cyclic hydrogen bonding in the neutral structures, the OH group o HSO{sub 4}{sup {minus}} in the ion-pair structures remains dangling because the counterion H{sub 2}O{sup +} prefers to make strong hydrogen bonds with water molecules and/or the HSO{sub 4}{sup {minus}} moiety.},
doi = {10.1021/jp984759x},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
number = 18,
volume = 103,
place = {United States},
year = {1999},
month = {5}
}