Ab initio theory of the nonequilibrium adsorption energy  

作　　者：Juho Lee Hyeonwoo Yeo Ryong-Gyu Lee Yong-Hoon Kim 

机构地区：[1]School of Electrical Engineering,Korea Advanced Institute of Science and Technology(KAIST),291 Daehak-ro,Yuseong-gu,Daejeon 34141,Republic of Korea

出　　处：《npj Computational Materials》2024年第1期2615-2621,共7页计算材料学(英文)

基　　金：supported by the National Research Foundation of Korea(2023R1A2C2003816,2022K1A3A1A91094293,RS-2023-00253716);the Samsung Research Funding&Incubation Center of Samsung Electronics(No.SRFC-TA2003-01);the BK21 Plus in the Korea Advanced Institute of Science and Technology;Computational resources were provided by the KISTI Supercomputing Center(KSC-2022-CRE-0258).

摘　　要：While first-principles calculations of electrode-molecule adsorption play an indispensable role in obtaining atomic-level understanding in surface science and electrochemistry,a significant challenge remains because the adsorption energy is well-defined only in equilibrium.Herein,a theory to calculate the electric enthalpy for electrified interfaces is formulated within the multi-space constrained-search density functional theory(MS-DFT),which provides the nonequilibrium total energy of a nanoscale electrode-channel-electrode junction.An additional MS-DFT calculation for the electrode-only counterpart that maintains the same bias voltage allows one to identify the internal energy of the channel as well as the electric field and the channel polarization,which together determine the electric enthalpy and the nonequilibrium adsorption energy.Application of the developed scheme to the water-Au and water-graphene interface models shows that the Au and graphene electrodes induce very different behaviors in terms of the electrode potential-dependent stabilization of water configurations.The theory developed here will be a valuable tool in the ongoing effort to obtain atomicscale understanding of bias-dependent molecular reorganizations in electrified interfaces.

关 键 词：ADSORPTION NONEQUILIBRIUM ELECTRODE 

分 类 号：O64[理学—物理化学]