Hydration, acidity and metal complexing of polysulfide species: a first principles molecular dynamics study

Xiandong Liu; Michiel Sprik; Jun Cheng

doi:10.1016/j.cplett.2013.01.046

Hydration, acidity and metal complexing of polysulfide species: a first principles molecular dynamics study

Xiandong Liu^*
, Michiel Sprik
, Jun Cheng

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

22 Citations (Scopus)

Abstract

We report a first principles molecular dynamics study on hydration and acidity of polysulfide species. Hydration structures of (poly)sulfides species are pictured by analyzing the trajectories. With the vertical energy gap technique, our calculations reproduce the acidity constants of H2S and predict chain length independent acidity for polysulfanes: pKa(1)s are about 7.0 and pKa(2)s are around 9.0. This indicates H2Sn, HSn and S-n(2) can all be dominant under common pH. Furthermore, our simulations show that stable Au+-HSn complexes can form in solutions, which implies that polysulfides can perform as metal complexing agents in hydrothermal processes. (C) 2013 Elsevier B. V. All rights reserved.

Original language	English
Pages (from-to)	9-14
Number of pages	6
Journal	Chemical Physics Letters
Volume	563
Early online date	4 Feb 2013
DOIs	https://doi.org/10.1016/j.cplett.2013.01.046
Publication status	Published - 20 Mar 2013

Funding

We acknowledge the National Science Foundation of China (Nos. 41002013, 41222015 and 41273074), the PhD Programs Foundation of Ministry of Education of China (No. 20110091120042), Newton International Fellow program and the support from the State Key Laboratory for Mineral Deposits Research in Nanjing University (No. 2010-II-14). We are grateful to the High Performance Computing Center of Nanjing University for allowing us to use the IBM Blade cluster system.

Keywords

2nd dissociation-constant
aqueous-solutions
sulfide solutions
hydrogen-sulfide
geologic role
PK(A) values
density
sulfur
surface
fluids

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10.1016/j.cplett.2013.01.046

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title = "Hydration, acidity and metal complexing of polysulfide species: a first principles molecular dynamics study",

abstract = "We report a first principles molecular dynamics study on hydration and acidity of polysulfide species. Hydration structures of (poly)sulfides species are pictured by analyzing the trajectories. With the vertical energy gap technique, our calculations reproduce the acidity constants of H2S and predict chain length independent acidity for polysulfanes: pKa(1)s are about 7.0 and pKa(2)s are around 9.0. This indicates H2Sn, HSn and S-n(2) can all be dominant under common pH. Furthermore, our simulations show that stable Au+-HSn complexes can form in solutions, which implies that polysulfides can perform as metal complexing agents in hydrothermal processes. (C) 2013 Elsevier B. V. All rights reserved.",

keywords = "2nd dissociation-constant, aqueous-solutions, sulfide solutions, hydrogen-sulfide, geologic role, PK(A) values, density, sulfur, surface, fluids",

author = "Xiandong Liu and Michiel Sprik and Jun Cheng",

year = "2013",

month = mar,

day = "20",

doi = "10.1016/j.cplett.2013.01.046",

language = "English",

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journal = "Chemical Physics Letters",

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TY - JOUR

T1 - Hydration, acidity and metal complexing of polysulfide species

T2 - a first principles molecular dynamics study

AU - Liu, Xiandong

AU - Sprik, Michiel

AU - Cheng, Jun

PY - 2013/3/20

Y1 - 2013/3/20

N2 - We report a first principles molecular dynamics study on hydration and acidity of polysulfide species. Hydration structures of (poly)sulfides species are pictured by analyzing the trajectories. With the vertical energy gap technique, our calculations reproduce the acidity constants of H2S and predict chain length independent acidity for polysulfanes: pKa(1)s are about 7.0 and pKa(2)s are around 9.0. This indicates H2Sn, HSn and S-n(2) can all be dominant under common pH. Furthermore, our simulations show that stable Au+-HSn complexes can form in solutions, which implies that polysulfides can perform as metal complexing agents in hydrothermal processes. (C) 2013 Elsevier B. V. All rights reserved.

AB - We report a first principles molecular dynamics study on hydration and acidity of polysulfide species. Hydration structures of (poly)sulfides species are pictured by analyzing the trajectories. With the vertical energy gap technique, our calculations reproduce the acidity constants of H2S and predict chain length independent acidity for polysulfanes: pKa(1)s are about 7.0 and pKa(2)s are around 9.0. This indicates H2Sn, HSn and S-n(2) can all be dominant under common pH. Furthermore, our simulations show that stable Au+-HSn complexes can form in solutions, which implies that polysulfides can perform as metal complexing agents in hydrothermal processes. (C) 2013 Elsevier B. V. All rights reserved.

KW - 2nd dissociation-constant

KW - aqueous-solutions

KW - sulfide solutions

KW - hydrogen-sulfide

KW - geologic role

KW - PK(A) values

KW - density

KW - sulfur

KW - surface

KW - fluids

U2 - 10.1016/j.cplett.2013.01.046

DO - 10.1016/j.cplett.2013.01.046

M3 - Article

SN - 0009-2614

VL - 563

SP - 9

EP - 14

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Hydration, acidity and metal complexing of polysulfide species: a first principles molecular dynamics study

Abstract

Funding

Keywords

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