Abstract
The oxidation mechanism of dimethylamine borane (DMAB), which acts as a reductant in the electroless deposition process, was studied using ab initio molecular orbital approaches such as Hartree-Fock (HF) and second order Møller-Plesset (MP2) calculations. The overall oxidation process of the DMAB was divided into each elementary reaction in which OH- substitutes H one by one and eventually forms B(OH)4 -. The oxidation mechanism of DMAB in the isolated state, which was previously proposed by us, was refined using more accurate basis sets, and the effects of solvation and interaction with metal surface sites on the oxidation mechanism were also studied. Taking the solvation effect into consideration using the self-consistent reaction field method with an isodensity polarized continuum model (SCRF-IPCM), the heat of oxidation was transferred to an exothermic reaction with decreasing dielectric constant. This indicated that the reaction preferably proceeds at the solid|liquid interface. Combined with Cu(111) and Pd(111) neutral cluster models as metal surface sites, it was found that the oxidation reaction proceeds preferentially at the metal surface sites. It was also suggested that the catalytic activity of the deposited metal is caused by its electron acceptivity.
| Original language | English |
|---|---|
| Pages (from-to) | 131-136 |
| Number of pages | 6 |
| Journal | Journal of Electroanalytical Chemistry |
| Volume | 559 |
| DOIs | |
| Publication status | Published - 2003 Nov 15 |
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Keywords
- Ab initio molecular orbital calculation
- Copper
- Dimethylamine borane
- Electroless deposition
- Metal nanostructure formation
- Palladium
- Reductant
ASJC Scopus subject areas
- Chemical Engineering(all)
- Analytical Chemistry
- Electrochemistry
Cite this
Molecular orbital study on the reaction process of dimethylamine borane as a reductant for electroless deposition. / Homma, Takayuki; Tamaki, Amiko; Nakai, Hiromi; Osaka, Tetsuya.
In: Journal of Electroanalytical Chemistry, Vol. 559, 15.11.2003, p. 131-136.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Molecular orbital study on the reaction process of dimethylamine borane as a reductant for electroless deposition
AU - Homma, Takayuki
AU - Tamaki, Amiko
AU - Nakai, Hiromi
AU - Osaka, Tetsuya
PY - 2003/11/15
Y1 - 2003/11/15
N2 - The oxidation mechanism of dimethylamine borane (DMAB), which acts as a reductant in the electroless deposition process, was studied using ab initio molecular orbital approaches such as Hartree-Fock (HF) and second order Møller-Plesset (MP2) calculations. The overall oxidation process of the DMAB was divided into each elementary reaction in which OH- substitutes H one by one and eventually forms B(OH)4 -. The oxidation mechanism of DMAB in the isolated state, which was previously proposed by us, was refined using more accurate basis sets, and the effects of solvation and interaction with metal surface sites on the oxidation mechanism were also studied. Taking the solvation effect into consideration using the self-consistent reaction field method with an isodensity polarized continuum model (SCRF-IPCM), the heat of oxidation was transferred to an exothermic reaction with decreasing dielectric constant. This indicated that the reaction preferably proceeds at the solid|liquid interface. Combined with Cu(111) and Pd(111) neutral cluster models as metal surface sites, it was found that the oxidation reaction proceeds preferentially at the metal surface sites. It was also suggested that the catalytic activity of the deposited metal is caused by its electron acceptivity.
AB - The oxidation mechanism of dimethylamine borane (DMAB), which acts as a reductant in the electroless deposition process, was studied using ab initio molecular orbital approaches such as Hartree-Fock (HF) and second order Møller-Plesset (MP2) calculations. The overall oxidation process of the DMAB was divided into each elementary reaction in which OH- substitutes H one by one and eventually forms B(OH)4 -. The oxidation mechanism of DMAB in the isolated state, which was previously proposed by us, was refined using more accurate basis sets, and the effects of solvation and interaction with metal surface sites on the oxidation mechanism were also studied. Taking the solvation effect into consideration using the self-consistent reaction field method with an isodensity polarized continuum model (SCRF-IPCM), the heat of oxidation was transferred to an exothermic reaction with decreasing dielectric constant. This indicated that the reaction preferably proceeds at the solid|liquid interface. Combined with Cu(111) and Pd(111) neutral cluster models as metal surface sites, it was found that the oxidation reaction proceeds preferentially at the metal surface sites. It was also suggested that the catalytic activity of the deposited metal is caused by its electron acceptivity.
KW - Ab initio molecular orbital calculation
KW - Copper
KW - Dimethylamine borane
KW - Electroless deposition
KW - Metal nanostructure formation
KW - Palladium
KW - Reductant
UR - http://www.scopus.com/inward/record.url?scp=0242573437&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0242573437&partnerID=8YFLogxK
U2 - 10.1016/S0022-0728(03)00042-1
DO - 10.1016/S0022-0728(03)00042-1
M3 - Article
AN - SCOPUS:0242573437
VL - 559
SP - 131
EP - 136
JO - Journal of Electroanalytical Chemistry
JF - Journal of Electroanalytical Chemistry
SN - 0022-0728
ER -