Bozhenko Konstantin V, Utenyshev Andrey N, Gutsev Lavrenty G, Aldoshin Sergey M, Gutsev Gennady L
Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, Academician Semenov Ave. 1, Chernogolovka, 142432, Russia.
Department of Physics, Florida A&M University, Tallahassee, Florida, 32307, USA.
J Mol Model. 2025 Jul 19;31(8):213. doi: 10.1007/s00894-025-06437-1.
Gas sensors with high sensitivity and selectivity are essential for industrial safety and environmental monitoring. The ongoing development of more effective sensors relies on two key aspects: the design of novel sensing materials and a deeper understanding of the underlying sensing mechanisms. Among the various materials used for the sensor fabrication, semiconducting metal oxides such as chromium and manganese oxides have garnered much recent attention. Notably, palladium-doped chromium oxide has demonstrated high efficiency in hydrogen sensing. Chromium oxides can function as single-component sensors and also in components of composite systems. Manganese oxides are likewise widely used in sensing applications, especially as electrochemical sensors either alone or in combination with other metal oxides.
All calculations were carried out by using spin-polarized density functional theory with the generalized gradient approximation as implemented in Gaussian 09. Among the numerous exchange-correlation functionals and basis sets, we chose the BPW91 functional and 6-311 + G* basis set of triple-zeta quality. We considered reactions of CrO and MnO with H and found pathways leading from the reagents to products. All but one reaction pathways were found to have two or three transition states separated by local minima. The search of transition states was performed by using the modified conjugate gradient algorithm and the local minima were determined by applying the intrinsic reaction coordinate algorithm. It was found that some of the pathways are spin-dependent, i.e., the total spin magnetic moments of reagents do not match those of the products.
具有高灵敏度和选择性的气体传感器对于工业安全和环境监测至关重要。更有效传感器的持续发展依赖于两个关键方面：新型传感材料的设计以及对潜在传感机制的更深入理解。在用于制造传感器的各种材料中，诸如氧化铬和氧化锰等半导体金属氧化物最近受到了广泛关注。值得注意的是，钯掺杂的氧化铬在氢气传感方面已显示出高效率。氧化铬既可以作为单组分传感器发挥作用，也可以用于复合系统的组件中。氧化锰同样广泛应用于传感应用，特别是单独或与其他金属氧化物结合用作电化学传感器。
所有计算均使用高斯09中实现的具有广义梯度近似的自旋极化密度泛函理论进行。在众多的交换相关泛函和基组中，我们选择了BPW91泛函和具有三重ζ质量的6 - 311 + G*基组。我们考虑了CrO和MnO与H的反应，并找到了从反应物到产物的反应途径。除了一个反应途径外，所有反应途径都被发现有两个或三个由局部极小值分隔的过渡态。通过使用改进的共轭梯度算法进行过渡态搜索，并通过应用内禀反应坐标算法确定局部极小值。结果发现，一些途径是自旋相关的，即反应物的总自旋磁矩与产物的总自旋磁矩不匹配。
