2在δ-Pu(100)表面的吸附行為。結(jié)果表明，CO2分子以C端向下和C-Pu、O-Pu多鍵結(jié)合的方式吸附在δ-Pu(100)表面。吸附類型屬于強(qiáng)化學(xué)吸附，最穩(wěn)定的吸附構(gòu)型是H1-C4O4，此時(shí)吸附能為-6.430 eV，吸附穩(wěn)定性順序?yàn)檠ㄎ?gt;橋位>頂位。CO2分子主要和表面Pu原子反應(yīng)，而與其它3層Pu原子的反應(yīng)較弱。更多的電子向CO2 2πu軌道轉(zhuǎn)移有利于C-O鍵的彎曲和活化。此外，CO2分子和Pu原子之間的化學(xué)鍵主要是離子態(tài)，反應(yīng)機(jī)理是CO2的C 2s、C 2p、O 2s 和O 2p軌道與Pu 6p、Pu 6d、Pu 5f軌道發(fā)生了重疊雜化作用，產(chǎn)生了新的鍵結(jié)構(gòu)。H1-C4O4構(gòu)型的功函數(shù)變化最小，表明其它電子容易從該構(gòu)型表面逃逸，且需要的能量最小。;A first-principles calculation was applied to study the adsorption behavior of CO2 on δ-Pu(100) surface using a slab model within the framework of density functional theory. Results demonstrate that CO2 molecules are adsorbed on δ-Pu(100) surface at C-terminated bent state by multi-bond binding of C-Pu and O-Pu. The adsorption type belongs to strong chemical adsorption and the most stable adsorption configuration is H1-C4O4 with the adsorption energy of -6.430 eV. The adsorption stability order is hollow site>bridge site>top site. CO2 molecule mainly interacts with Pu surface atoms, while the interaction with other three Pu atoms is weak. The transfer of more electrons to the CO2 2πu orbital is beneficial to the bending and activation of C-O bonds. Moreover, the chemical bonding between Pu atoms and CO2 molecule is mainly ionic state and the reaction mechanism is that the C 2s, C 2p, O 2s and O 2p orbitals of CO2 molecule hybrid with Pu 6p, Pu 6d and Pu 5f orbitals, resulting in a new bond structure. The work function of the H1-C4O4 site changes the least, indicating that other electrons readily escape from the metal surface and the required energy is the smallest."/>
2;密度泛函;電子密度;吸附行為;作用機(jī)理;plutonium surface;carbon dioxide;density functional theory;electron density;adsorption behavior;reaction mechanism"/>