Reactions of Zn(4s4p 3P1) and Cd(5s5p 3P1) with SiH4

Wang, J.‐H.; Umemoto, Hironobu; Leung, Allen W. K.; Breckenridge, W. H.

doi:10.1063/1.471685

Cited by 15 publications

(17 citation statements)

References 72 publications

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“…Some of these products are useful in the industry to get hydrogenated amorphous silicon ͑a-Si:H͒ among other applications. Breckenridge et al [24][25][26] studied the reactivity of excited metal atoms with SiH 4 molecules in the gas phase. Electronic mail: hpacheco@ittoluca.edu.mx.…”

Section: Introductionmentioning

confidence: 99%

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Pacheco-Sánchez

Luna‐García

García-Cruz

et al. 2010

The Journal of Chemical Physics

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Transition probabilities on the interaction of the ground and the lowest excited states of gold Au ((2)S:5d(10)6s(1), (2)D:5d(9)6s(2), and (2)P:5d(10)6p(1)) with silane (SiH(4)) are studied through ab initio Hartree-Fock self-consistent field calculations, where the atom's core is represented by relativistic effective core potentials. These calculations are followed by a multiconfigurational self-consistent field study. The correlation energy is accounted for through extensive variational and perturbative second order multireference Moller-Plesset configuration interaction analysis of selected perturbations obtained by iterative process calculations using the CIPSI program package. It is found that the Au atom in the ((2)P:5d(10)6p(1)) state inserts in the Si-H bond. In this interaction its corresponding D (2)A(') potential energy surface is initially attractive and only becomes repulsive after encountering an avoided crossing with the initially repulsive C (2)A(') surface linked to the Au((2)D:5d(9)6s(2))-SiH(4) fragments. The A, B, and C (2)A(') curves derived from the Au((2)D:5d(9)6s(2)) atom interaction with silane are initially repulsive, each one of them showing two avoided crossings, while the A (2)A(') curve goes sharply downwards until it meets the X (2)A(') curve interacting adiabatically, which is linked with the Au((2)S:5d(10)6s(1))-SiH(4) moieties. The A (2)A(') curve becomes repulsive after the avoided crossing with the X (2)A('), curve. The lowest-lying X (2)A(') potential leads to the HAuSiH(3) X (2)A(') intermediate molecule. This intermediate molecule, diabatically correlated with the Au((2)P:5d(10)6p(1))+SiH(4) system which lies 3.34 kcal/mol above the ground state reactants, has been carefully characterized as have the dissociation channels leading to the AuH+SiH(3) and H+AuSiH(3) products. These products are reached from the HAuSiH(3) intermediate without any activation barrier. The Au-SiH(4) calculation results are successfully compared to experiment. Landau-Zener theory of avoided crossings is applied to these interactions considering the angle theta instead of the distance r as the reaction coordinate.

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Section: Introductionmentioning

confidence: 99%

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Pacheco-Sánchez

Luna‐García

García-Cruz

et al. 2010

The Journal of Chemical Physics

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“…We have recently reported that both Cd(5s5p 3 P 1 ) and Zn(4s4p 3 P 1 ) readily activate Si−H bonds in SiH 4 , forming the metal hydride molecules and SiH 3 in the gas phase. In contrast, these reagents 1,2,4,5,13,15,49-51 [as well as the analogous Hg(6s6p 3 P 0,1 ) states 1,2,4,5 ] are very inefficient in activating the C−H bonds in CH 4 .…”

Section: Introductionmentioning

confidence: 99%

Activation of H−H, Si−H, and C−H Bonds bynsnp Excited States of Metal Atoms

1996

Self Cite

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We present a comprehensive overview of our current knowledge of the interactions of valence M(nsnp 3P) and M(nsnp 1P1) excited states with H−H, Si−H, and C−H bonds, where M = Mg, Zn, Cd, and Hg. It is proposed that the high reactivity of M(nsnp 3P1) states with H−H and Si−H bonds compared to C−H bonds is due to the lack of steric hindrance in the localized, side-on, M(npπ)−XH(σ*) donor−acceptor molecular orbital interactions, since the Si−H bond length in SiH4 is ∼1.5 Å compared to C−H bond lengths of ∼1.1 Å. It is also concluded that Mg(3s3p 1P1) and Zn(4s4p 1P1) efficiently activate C−H bonds as well as H−H and Si−H bonds not just because of their higher energy but because of better M(npπ)−XH(σ*) energy matches and overlap, which overcomes M(ns)−XH(σ) repulsion and the steric hindrance. It is further proposed that the striking differences in the microscopic mechanisms of attack of C−H bonds by Mg(1P1) versus Zn(1P1) may be due to the fact that the Zn(4s) “core” is substantially (∼0.2 Å) smaller than the Mg(3s) “core”, allowing true insertion of the Zn(1P1) state (but not the Mg(1P1) state) into C−H bonds to form (by surface hopping) long-lived ground-state zinc alkyl hydrides which decompose in a non-RRKM fashion to yield the observed ZnH product. Finally, the experimental results to date (as well as ab initio calculations) indicate that direct, end-on “abstractive” attack of M(nsnp 1P1) states [as well as O(1D2)] of H−H, Si−H, and C−H bonds probably does not occur.

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“…By using the pump–probe technique, Breckenridge and co-workers have thoroughly investigated the reactions of n s n p metal atoms with H 2 , CH 4 , SiH 4 , and GeH 4 in the gas phase . The experimental and theoretical studies suggest that the reactions of the n s n p ( 1 P) excited-state group II metal atoms with EH 4 (E = C, Si, Ge) molecules favored the side-on insertion mechanism instead of direct abstraction of H from EH 4 by end-on attack of the E–H bond. − The reactions of methane with naked metal atoms have been widely studied using the matrix isolation technique. In the low-temperature noble gas matrix, laser-ablated group IIA (Be, Mg, and Ca) and group IIB (Zn, Cd, and Hg) metal atoms react with methane upon photolysis, leading to the formation of HMCH 3 molecules.…”

Section: Introductionmentioning

confidence: 99%

Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)₃E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies

Zhao

Xiao

et al. 2020

Inorg. Chem.

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Matrix isolation infrared spectroscopy combined with quantumchemical calculations were employed to study the reactions of calcium atoms with silane, germane, and stannane in a 4 K argon matrix. The ion pairs [HCa] + and [EH 3 ] − (E = Si, Ge, and Sn) in both the classical structure HCaEH 3 and the bridged structure HCa(μ-H) 3 E were identified based on the H/D isotopic substitution experiments and quantum-chemical calculations. The results show that the reaction between ground-state Ca and EH 4 proceeds inefficiently, and only after the photolytic activation of Ca atoms to the Ca( 1 P:4s4p) state does insertion occur to give HCaEH 3 , which rearranges to HCa(μ-H) 3 E upon photolysis. Topological analysis of the electronic structure suggests that the nonclassical structure HCa(μ-H) 3 E is formed by the electrostatic interaction with charge-inverted hydrogen bridge bond, while HCaEH 3 is dominated by (HCa) + (EH 3 ) − ion pair interactions.

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Reactions of Zn(4s4p 3P1) and Cd(5s5p 3P1) with SiH4

Abstract: Electron states of benzene-Br2 donor-acceptor complex: HeI photoelectron spectroscopy and ab initio molecular orbital study

Cited by 15 publications

References 72 publications

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Activation of H−H, Si−H, and C−H Bonds bynsnp Excited States of Metal Atoms

Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)₃E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies

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Reactions of Zn(4s4p 3P1) and Cd(5s5p 3P1) with SiH4

Abstract: Electron states of benzene-Br2 donor-acceptor complex: HeI photoelectron spectroscopy and ab initio molecular orbital study

Cited by 15 publications

References 72 publications

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Activation of H−H, Si−H, and C−H Bonds bynsnp Excited States of Metal Atoms

Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)3E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies

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Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)₃E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies