Kinetical and thermodynamical analysis of the reactivity of thiourea by association to Ca2+

Cristina Trujillo; José A. Gámez

doi:10.1016/j.comptc.2014.11.018

Kinetical and thermodynamical analysis of the reactivity of thiourea by association to Ca²⁺

Cristina Trujillo, José A. Gámez^*

^*Corresponding author for this work

Computational and Theoretical Chemistry

Max-Planck-Institut für Kohlenforschung

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

Abstract

We have carried out a computational study on the kinetics of the reaction between Ca²⁺ and TU. The most preferred product from the kinetical point of view is the Coulomb explosion yielding TU⁺ and Ca⁺. This observation totally agrees with the MS/MS spectra of [CaTU]²⁺ complex and complements the conclusions drawn from the analysis of the Potential Energy Surface (PES). Contrary to [CaTU]²⁺, the process with the highest yield in [CaU]⁺ is the release of NH₃. This dissimilar reactivity of U and TU towards Ca²⁺ is attributed to the lowest ionization potential of thiourea with respect to that of urea.

Original language	English
Pages (from-to)	68-72
Number of pages	5
Journal	Computational and Theoretical Chemistry
Volume	1052
Early online date	27 Nov 2014
DOIs	https://doi.org/10.1016/j.comptc.2014.11.018
Publication status	Published - 5 Jan 2015

Keywords

calcium
dications
kinetics
RRKM
thiourea
urea

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10.1016/j.comptc.2014.11.018

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title = "Kinetical and thermodynamical analysis of the reactivity of thiourea by association to Ca2+",

abstract = "We have carried out a computational study on the kinetics of the reaction between Ca2+ and TU. The most preferred product from the kinetical point of view is the Coulomb explosion yielding TU+ and Ca+. This observation totally agrees with the MS/MS spectra of [CaTU]2+ complex and complements the conclusions drawn from the analysis of the Potential Energy Surface (PES). Contrary to [CaTU]2+, the process with the highest yield in [CaU]+ is the release of NH3. This dissimilar reactivity of U and TU towards Ca2+ is attributed to the lowest ionization potential of thiourea with respect to that of urea.",

keywords = "calcium, dications, kinetics, RRKM, thiourea, urea",

author = "Cristina Trujillo and G{\'a}mez, {Jos{\'e} A.}",

note = "Funding Information: This work has been partially supported by the DGI Project No. CTQ2006-08558/BQU, by the Project MADRISOLAR, Ref.: S-0505/PPQ/0225 of the Universidad Aut{\'o}noma de Madrid. JAG acknowledges a postdoctoral fellowship from the Alexander von Humboldt Stiftung. Dr. A. Cimas is also acknowledged for helpful comments and discussion. A generous allocation of computing time at the CCC of the UAM is also acknowledged. Publisher Copyright: {\textcopyright} 2014 Elsevier B.V.",

year = "2015",

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doi = "10.1016/j.comptc.2014.11.018",

language = "English",

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TY - JOUR

T1 - Kinetical and thermodynamical analysis of the reactivity of thiourea by association to Ca2+

AU - Trujillo, Cristina

AU - Gámez, José A.

N1 - Funding Information: This work has been partially supported by the DGI Project No. CTQ2006-08558/BQU, by the Project MADRISOLAR, Ref.: S-0505/PPQ/0225 of the Universidad Autónoma de Madrid. JAG acknowledges a postdoctoral fellowship from the Alexander von Humboldt Stiftung. Dr. A. Cimas is also acknowledged for helpful comments and discussion. A generous allocation of computing time at the CCC of the UAM is also acknowledged. Publisher Copyright: © 2014 Elsevier B.V.

PY - 2015/1/5

Y1 - 2015/1/5

N2 - We have carried out a computational study on the kinetics of the reaction between Ca2+ and TU. The most preferred product from the kinetical point of view is the Coulomb explosion yielding TU+ and Ca+. This observation totally agrees with the MS/MS spectra of [CaTU]2+ complex and complements the conclusions drawn from the analysis of the Potential Energy Surface (PES). Contrary to [CaTU]2+, the process with the highest yield in [CaU]+ is the release of NH3. This dissimilar reactivity of U and TU towards Ca2+ is attributed to the lowest ionization potential of thiourea with respect to that of urea.

AB - We have carried out a computational study on the kinetics of the reaction between Ca2+ and TU. The most preferred product from the kinetical point of view is the Coulomb explosion yielding TU+ and Ca+. This observation totally agrees with the MS/MS spectra of [CaTU]2+ complex and complements the conclusions drawn from the analysis of the Potential Energy Surface (PES). Contrary to [CaTU]2+, the process with the highest yield in [CaU]+ is the release of NH3. This dissimilar reactivity of U and TU towards Ca2+ is attributed to the lowest ionization potential of thiourea with respect to that of urea.

KW - calcium

KW - dications

KW - kinetics

KW - RRKM

KW - thiourea

KW - urea

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U2 - 10.1016/j.comptc.2014.11.018

DO - 10.1016/j.comptc.2014.11.018

M3 - Article

AN - SCOPUS:84918836143

SN - 2210-271X

VL - 1052

SP - 68

EP - 72

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

ER -

Kinetical and thermodynamical analysis of the reactivity of thiourea by association to Ca²⁺

Abstract

Keywords

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