当前位置：
X-MOL 学术
›
Inorg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
DFT Study of α-Keggin-type Iso-polyoxotungstate Anions [HnW12O40](8–n)– (n =1–4): Can [H4W12O40]4– Exist?
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-09-27 , DOI: 10.1021/acs.inorgchem.1c01962 Kazuo Eda 1 , Masahiko Akune 1 , Chie Yasuma 1 , Hiroki Hotta 2 , Toshiyuki Osakai 1 , Takahito Nakajima 1, 3
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-09-27 , DOI: 10.1021/acs.inorgchem.1c01962 Kazuo Eda 1 , Masahiko Akune 1 , Chie Yasuma 1 , Hiroki Hotta 2 , Toshiyuki Osakai 1 , Takahito Nakajima 1, 3
Affiliation
|
The Keggin-type iso-polyoxotungstate (iso-POT) anions [HnW12O40](8–n)– ’s, in which their central vacancies are occupied by protons, are attractive materials. It is of importance to reveal if the vacancies can be fully occupied by four protons. For further understanding the speciation of these iso-POT anions, relative stabilities and proton transfer reactions between H1[Hn–1W12O40](8–n)– and [HnW12O40](8–n)– were examined in detail by using the first-principles calculations (the nudged elastic band method, the synchronous transit-guided quasi-Newton method, the intrinsic reaction coordinate method, and frequency analysis calculations). Thermochemistry analysis of the proton transfer was also performed. [HnW12O40](8–n)– was energetically more stable than H1[Hn–1W12O40](8–n)–. This held for n = 4. According to the results of thermochemistry analysis, the rate constant and the Wigner correction were respectively 3.1 × 101 s–1 and 2.2 at T = 298.15 K for the proton transfer from H1[H3W12O40]4– to [H4W12O40]4–, indicating that [H4W12O40]4– can exist when H1[H3W12O40]4– is formed by protonating [H3W12O40]5–.
中文翻译：
α-Keggin 型异多钨酸盐阴离子 [HnW12O40](8–n)– (n =1–4) 的 DFT 研究：[H4W12O40]4– 是否存在？
Keggin 型异多氧钨酸盐 (iso-POT) 阴离子 [H n W 12 O 40 ] (8– n )–的中心空位被质子占据，是有吸引力的材料。揭示空位是否可以被四个质子完全占据是很重要的。为了进一步了解这些 iso-POT 阴离子的形态、相对稳定性和 H 1 [H n –1 W 12 O 40 ] (8– n )–和 [H n W 12 O 40 ] (8– n )–通过使用第一性原理计算（轻推弹性带法、同步过渡引导的拟牛顿法、本征反应坐标法和频率分析计算）详细检查了它们。还进行了质子转移的热化学分析。[H n W 12 O 40 ] (8– n )–在能量上比 H 1 [H n –1 W 12 O 40 ] (8– n )–更稳定。这对n = 4 成立。根据热化学分析的结果，速率常数和 Wigner 校正分别为 3.1 × 10从 H 1 [H 3 W 12 O 40 ] 4–到 [H 4 W 12 O 40 ] 4–的质子转移在T = 298.15 K 时为1 s –1和 2.2 ，表明 [H 4 W 12 O 40 ]当 H 1 [H 3 W 12 O 40 ] 4-通过质子化 [H 3 W 12 O 40 ] 5-形成时，4-可以存在。
更新日期：2021-10-18
中文翻译：
α-Keggin 型异多钨酸盐阴离子 [HnW12O40](8–n)– (n =1–4) 的 DFT 研究：[H4W12O40]4– 是否存在？
Keggin 型异多氧钨酸盐 (iso-POT) 阴离子 [H n W 12 O 40 ] (8– n )–的中心空位被质子占据，是有吸引力的材料。揭示空位是否可以被四个质子完全占据是很重要的。为了进一步了解这些 iso-POT 阴离子的形态、相对稳定性和 H 1 [H n –1 W 12 O 40 ] (8– n )–和 [H n W 12 O 40 ] (8– n )–通过使用第一性原理计算（轻推弹性带法、同步过渡引导的拟牛顿法、本征反应坐标法和频率分析计算）详细检查了它们。还进行了质子转移的热化学分析。[H n W 12 O 40 ] (8– n )–在能量上比 H 1 [H n –1 W 12 O 40 ] (8– n )–更稳定。这对n = 4 成立。根据热化学分析的结果，速率常数和 Wigner 校正分别为 3.1 × 10从 H 1 [H 3 W 12 O 40 ] 4–到 [H 4 W 12 O 40 ] 4–的质子转移在T = 298.15 K 时为1 s –1和 2.2 ，表明 [H 4 W 12 O 40 ]当 H 1 [H 3 W 12 O 40 ] 4-通过质子化 [H 3 W 12 O 40 ] 5-形成时，4-可以存在。
京公网安备 11010802027423号