Pressure Dependence of Rate Coefficients for Formation and Dissociation of Pentachlorodisilane and Related Chemical Activation Reactions

Kaito Noda, Nilson Kunioshi, Akio Fuwa

    研究成果: Article

    抄録

    Four entrance channels to the pentachlorodisilane (Si2HCl5) potential energy well, namely, SiCl2 + SiHCl3, SiCl4 + SiHCl, Cl3SiSiCl + HCl, and SiCl3 + SiHCl2, were analyzed in detail through transition state theory, Rice–Ramsperger–Kassel–Marcus (RRKM) theory, and solution of the multichannel master equation. The stationary points in the potential energy surface were optimized, and their vibrational frequencies and rotational constants calculated at the (U)B3LYP/6–31+G(d,p) level of theory; the (U)CCSD(T)/aug-cc-pVTZ level was then used for accurate estimation of activation energies. The pressure and temperature dependence of the rate coefficients of the channels related to Si2HCl5 stabilization/dissociation was determined along a wide range of conditions, for the first time. All channels showed strong pressure dependence in the four cases, at least at low-to-moderate pressure conditions. Each entrance channel leads to the formation of different products under different conditions, and the mechanism was analyzed in detail. The results indicated that at atmospheric pressure the reactions are in the falloff region, and therefore do not support the adoption of high-pressure limit rate coefficients in reaction models designed for simulation of systems at atmospheric or subatmospheric pressure conditions.

    元の言語English
    ページ(範囲)584-595
    ページ数12
    ジャーナルInternational Journal of Chemical Kinetics
    49
    発行部数8
    DOI
    出版物ステータスPublished - 2017 8 1

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    pressure dependence
    Chemical activation
    activation
    dissociation
    Pressure
    coefficients
    entrances
    atmospheric pressure
    potential energy
    Potential energy surfaces
    Atmospheric Pressure
    Vibrational spectra
    Potential energy
    stabilization
    Atmospheric pressure
    activation energy
    Stabilization
    temperature dependence
    Activation energy
    products

    ASJC Scopus subject areas

    • Biochemistry
    • Physical and Theoretical Chemistry
    • Organic Chemistry
    • Inorganic Chemistry

    これを引用

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    abstract = "Four entrance channels to the pentachlorodisilane (Si2HCl5) potential energy well, namely, SiCl2 + SiHCl3, SiCl4 + SiHCl, Cl3SiSiCl + HCl, and SiCl3 + SiHCl2, were analyzed in detail through transition state theory, Rice–Ramsperger–Kassel–Marcus (RRKM) theory, and solution of the multichannel master equation. The stationary points in the potential energy surface were optimized, and their vibrational frequencies and rotational constants calculated at the (U)B3LYP/6–31+G(d,p) level of theory; the (U)CCSD(T)/aug-cc-pVTZ level was then used for accurate estimation of activation energies. The pressure and temperature dependence of the rate coefficients of the channels related to Si2HCl5 stabilization/dissociation was determined along a wide range of conditions, for the first time. All channels showed strong pressure dependence in the four cases, at least at low-to-moderate pressure conditions. Each entrance channel leads to the formation of different products under different conditions, and the mechanism was analyzed in detail. The results indicated that at atmospheric pressure the reactions are in the falloff region, and therefore do not support the adoption of high-pressure limit rate coefficients in reaction models designed for simulation of systems at atmospheric or subatmospheric pressure conditions.",
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    AU - Noda, Kaito

    AU - Kunioshi, Nilson

    AU - Fuwa, Akio

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    Y1 - 2017/8/1

    N2 - Four entrance channels to the pentachlorodisilane (Si2HCl5) potential energy well, namely, SiCl2 + SiHCl3, SiCl4 + SiHCl, Cl3SiSiCl + HCl, and SiCl3 + SiHCl2, were analyzed in detail through transition state theory, Rice–Ramsperger–Kassel–Marcus (RRKM) theory, and solution of the multichannel master equation. The stationary points in the potential energy surface were optimized, and their vibrational frequencies and rotational constants calculated at the (U)B3LYP/6–31+G(d,p) level of theory; the (U)CCSD(T)/aug-cc-pVTZ level was then used for accurate estimation of activation energies. The pressure and temperature dependence of the rate coefficients of the channels related to Si2HCl5 stabilization/dissociation was determined along a wide range of conditions, for the first time. All channels showed strong pressure dependence in the four cases, at least at low-to-moderate pressure conditions. Each entrance channel leads to the formation of different products under different conditions, and the mechanism was analyzed in detail. The results indicated that at atmospheric pressure the reactions are in the falloff region, and therefore do not support the adoption of high-pressure limit rate coefficients in reaction models designed for simulation of systems at atmospheric or subatmospheric pressure conditions.

    AB - Four entrance channels to the pentachlorodisilane (Si2HCl5) potential energy well, namely, SiCl2 + SiHCl3, SiCl4 + SiHCl, Cl3SiSiCl + HCl, and SiCl3 + SiHCl2, were analyzed in detail through transition state theory, Rice–Ramsperger–Kassel–Marcus (RRKM) theory, and solution of the multichannel master equation. The stationary points in the potential energy surface were optimized, and their vibrational frequencies and rotational constants calculated at the (U)B3LYP/6–31+G(d,p) level of theory; the (U)CCSD(T)/aug-cc-pVTZ level was then used for accurate estimation of activation energies. The pressure and temperature dependence of the rate coefficients of the channels related to Si2HCl5 stabilization/dissociation was determined along a wide range of conditions, for the first time. All channels showed strong pressure dependence in the four cases, at least at low-to-moderate pressure conditions. Each entrance channel leads to the formation of different products under different conditions, and the mechanism was analyzed in detail. The results indicated that at atmospheric pressure the reactions are in the falloff region, and therefore do not support the adoption of high-pressure limit rate coefficients in reaction models designed for simulation of systems at atmospheric or subatmospheric pressure conditions.

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