DFT and CCSD(T) study of the disilicon trihydride (Si2H3) isomerization, unprecedented isomeric structures

Choukri, Hasna; Guermoune, Abdeladim; Schmitzer, Andreea R.; Villemin, Didier; Cherqaoui, Driss; Jarid, Abdellah

doi:10.1016/j.theochem.2007.12.013

Cited by 3 publications

(3 citation statements)

References 24 publications

(36 reference statements)

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“…Table S2 in the Supporting Information shows that the theoretical and experimental frequencies and rotational constants of SiH 4 agrees within 2%. For the H 2 SiSiH and the H 3 SiSi isomers, our structural parameters are very consistent with previous theoretical predictions [45,47]. n/i-Si 3 H 7 Decomposition.…”

Section: Sih 4 + H 2 Sisih/sisih 3 Association Each Reactionsupporting

confidence: 91%

“…In a previous study , although the H 2 SiSiH isomer was reported to have a higher energy of 5.5 kcal/mol than the SiSiH 3 isomer at the self‐consistent field (SCF) level, but at higher levels of theory considering full triples, with relativistic and ZVPE corrections, the H 2 SiSiH isomer was found to be more stable than the SiSiH 3 isomer. Choukri et al also showed that the former is lower in energy by 0.04–0.67 kcal/mol than the latter. In our study at the CCSD(T)/CBS//B3LYP/6–311++G(3df,2p) level, we found that the H 2 SiSiH isomer is 0.5 kcal/mol more stable than the SiSiH 3 isomer, in good agreement with the recent literature value.…”

Section: Resultsmentioning

confidence: 97%

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Ab Initio Chemical Kinetics for SiH_xReactions with Si₂H_y(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Nguyen

Lin

2017

Int. J. Chem. Kinet.

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Gas‐phase reactions of SiHx with Si2Hy (x = 1,2,3,4; y = 6,5,4,3) species, respectively, which may coexist under chemical vapor deposition (CVD) conditions, have been investigated by means of ab initio molecular orbital and statistical theory calculations. Potential energy surface (PES) predicted at the CCSD(T)/CBS//B3LYP/6–311++G(3df,2p) level shows that these reactions take place primarily via trisilany radicals, n‐Si3H7 and i‐Si3H7. For example, SiH2 can associate with Si2H5 producing n‐H2SiSiH2SiH3 exothermically by 55.8 kcal/mol; SiH3 can undergo addition to H2SiSiH2 to produce n‐Si3H7 or associate with H3SiSiH barrierlessly forming i‐Si3H7; whereas SiH can insert into one of the Si─H bonds of Si2H6 to give excited n‐Si3H7. Similarly, H2SiSiH and SiSiH3 can undergo insertion reactions with SiH4 producing n/i‐Si3H7 intermediates, respectively, to be followed by fragmentation to various smaller species. These processes are fully depicted in the complete PES. The predicted heats of formation of various species agree well with available thermochemical data. The rate constants and product branching ratios for the low‐energy channel products have been calculated for the temperature range 300–1000 K by variational RRKM (Rice–Ramsperger–Kassel–Macus) theory with Eckart tunneling corrections. The results may be employed for realistic kinetic modeling of the plasma‐enhanced chemical vapor deposition growth of a‐Si:H thin films under practical conditions.

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Section: Sih 4 + H 2 Sisih/sisih 3 Association Each Reactionsupporting

confidence: 91%

Section: Resultsmentioning

confidence: 97%

Ab Initio Chemical Kinetics for SiH_xReactions with Si₂H_y(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Nguyen

Lin

2017

Int. J. Chem. Kinet.

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“…Among the six Si 2 H 3 isomers ( 25 – 30 ), silylsilylidyne (H 3 SiSi; 26 ; X 2 A), vinyl-type disilenyl (H 2 SiSiH; 27 ; X 2 A), and one monobridged isomer Si(H)SiH 2 ( 25 ; X 2 A″) are nearly isoenergetic. The hydrogen atoms of disilenyl are slightly bent out-of-plane, and thus there is no symmetry at all; this reflects the diverse chemistry of silicon versus carbon and germanium. − Considering the unusual silicon and germanium bearing mono- and dibridged HGe(μ-H)SiH ( 13 ; X 2 A), Ge(μ-H 2 )SiH ( 15 ; X 2 A′), HGe(μ-H)SiH ( 16 ; X 2 A), HGe(μ-H 2 )Si ( 18 ; X 2 A′), H 2 Ge(μ-H)Ge ( 21 ; X 2 A″), HGe(μ-H)GeH ( 22 ; X 2 A), HGe(μ-H 2 )Ge ( 23 ; X 2 A′), HGe(μ-H)GeH ( 24 ; X 2 A), H 2 Si(μ-H)Si ( 25 ; X 2 A″), HSi(μ-H)SiH ( 28 ; X 2 A), HSi(μ-H)SiH ( 29 ; X 2 A), and HSi(μ-H 2 )Si ( 30 ; X 2 A′) isomers, whose carbon analogue structures do not exist, the special molecular structure and chemical bonding of heavy main group XIV elements are also reflected.…”

Section: Introductionmentioning

confidence: 99%

Combined Experimental and Computational Study on the Reaction Dynamics of the D1-Silylidyne(SiD) – Silane (SiH₄) System

Yang

Sun

et al. 2021

J. Phys. Chem. A

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Small silicon hydrides have attracted extensive interest because of their role in the chemical evolution of circumstellar envelopes of evolved carbon stars and applications in surface growth processes and as transients in semiconductor manufacturing. Combined with electronic structure calculations, we demonstrate that monobridged silylidynesilylenes [(Si(μ-D)SiH 2 , Si(μ-H)SiHD, Si(μ-H)SiH 2 ] and silylsilylidyne [H 3 SiSi, H 2 DSiSi], which are nearly isoenergetic, can be prepared via molecular hydrogen loss channels in the crossed molecular beam study of the reaction of D1-silylidyne (SiD; X 2 Π) with silane (SiH 4 ; X 1 A 1 ) in a crossed molecular beams machine. Compared to the dynamics of the isovalent methylidyne (CH) − methane (CH 4 ) system, our study delivers a unique view at the intriguing isomerization processes and reaction dynamics of dinuclear silicon hydride transients, thus contributing to our knowledge on the chemical bonding of silicon hydrides at the molecular level.

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Directed Gas Phase Formation of the Elusive Silylgermylidyne Radical (H₃SiGe, X²A′′)

et al. 2020

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The previously unknown silylgermylidyne radical (H3SiGe; X2A′′) was prepared via the bimolecular gas phase reaction of ground state silylidyne radicals (SiH; X2Π) with germane (GeH4; X1A1) under single collision conditions in crossed molecular beams experiments. This reaction begins with the formation of a van der Waals complex followed by insertion of silylidyne into a germanium‐hydrogen bond forming the germylsilyl radical (H3GeSiH2). A hydrogen migration isomerizes this intermediate to the silylgermyl radical (H2GeSiH3), which undergoes a hydrogen shift to an exotic, hydrogen‐bridged germylidynesilane intermediate (H3Si(μ‐H)GeH); this species emits molecular hydrogen forming the silylgermylidyne radical (H3SiGe). Our study offers a remarkable glance at the complex reaction dynamics and inherent isomerization processes of the silicon‐germanium system, which are quite distinct from those of the isovalent hydrocarbon system (ethyl radical; C2H5) eventually affording detailed insights into an exotic chemistry and intriguing chemical bonding of silicon‐germanium species at the microscopic level exploiting crossed molecular beams.

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DFT and CCSD(T) study of the disilicon trihydride (Si2H3) isomerization, unprecedented isomeric structures

Cited by 3 publications

References 24 publications

Ab Initio Chemical Kinetics for SiH_xReactions with Si₂H_y(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Ab Initio Chemical Kinetics for SiH_xReactions with Si₂H_y(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Combined Experimental and Computational Study on the Reaction Dynamics of the D1-Silylidyne(SiD) – Silane (SiH₄) System

Directed Gas Phase Formation of the Elusive Silylgermylidyne Radical (H₃SiGe, X²A′′)

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DFT and CCSD(T) study of the disilicon trihydride (Si2H3) isomerization, unprecedented isomeric structures

Cited by 3 publications

References 24 publications

Ab Initio Chemical Kinetics for SiHxReactions with Si2Hy(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Ab Initio Chemical Kinetics for SiHxReactions with Si2Hy(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Combined Experimental and Computational Study on the Reaction Dynamics of the D1-Silylidyne(SiD) – Silane (SiH4) System

Directed Gas Phase Formation of the Elusive Silylgermylidyne Radical (H3SiGe, X2A′′)

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Product

Resources

About

Ab Initio Chemical Kinetics for SiH_xReactions with Si₂H_y(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Ab Initio Chemical Kinetics for SiH_xReactions with Si₂H_y(x= 1,2,3,4;y= 6,5,4,3;x+y= 7) under a-Si:H CVD Condition

Combined Experimental and Computational Study on the Reaction Dynamics of the D1-Silylidyne(SiD) – Silane (SiH₄) System

Directed Gas Phase Formation of the Elusive Silylgermylidyne Radical (H₃SiGe, X²A′′)