The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulati...The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures.AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased.Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction.The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels.We provided explanations consistent with the principles of thermodynamics and statistical physics.The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments.展开更多
To address the seismic face stability challenges encountered in urban and subsea tunnel construction,an efficient probabilistic analysis framework for shield tunnel faces under seismic conditions is proposed.Based on ...To address the seismic face stability challenges encountered in urban and subsea tunnel construction,an efficient probabilistic analysis framework for shield tunnel faces under seismic conditions is proposed.Based on the upper-bound theory of limit analysis,an improved three-dimensional discrete deterministic mechanism,accounting for the heterogeneous nature of soil media,is formulated to evaluate seismic face stability.The metamodel of failure probabilistic assessments for seismic tunnel faces is constructed by integrating the sparse polynomial chaos expansion method(SPCE)with the modified pseudo-dynamic approach(MPD).The improved deterministic model is validated by comparing with published literature and numerical simulations results,and the SPCE-MPD metamodel is examined with the traditional MCS method.Based on the SPCE-MPD metamodels,the seismic effects on face failure probability and reliability index are presented and the global sensitivity analysis(GSA)is involved to reflect the influence order of seismic action parameters.Finally,the proposed approach is tested to be effective by a engineering case of the Chengdu outer ring tunnel.The results show that higher uncertainty of seismic response on face stability should be noticed in areas with intense earthquakes and variation of seismic wave velocity has the most profound influence on tunnel face stability.展开更多
文摘The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures.AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased.Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction.The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels.We provided explanations consistent with the principles of thermodynamics and statistical physics.The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments.
基金Project([2018]3010)supported by the Guizhou Provincial Science and Technology Major Project,China。
文摘To address the seismic face stability challenges encountered in urban and subsea tunnel construction,an efficient probabilistic analysis framework for shield tunnel faces under seismic conditions is proposed.Based on the upper-bound theory of limit analysis,an improved three-dimensional discrete deterministic mechanism,accounting for the heterogeneous nature of soil media,is formulated to evaluate seismic face stability.The metamodel of failure probabilistic assessments for seismic tunnel faces is constructed by integrating the sparse polynomial chaos expansion method(SPCE)with the modified pseudo-dynamic approach(MPD).The improved deterministic model is validated by comparing with published literature and numerical simulations results,and the SPCE-MPD metamodel is examined with the traditional MCS method.Based on the SPCE-MPD metamodels,the seismic effects on face failure probability and reliability index are presented and the global sensitivity analysis(GSA)is involved to reflect the influence order of seismic action parameters.Finally,the proposed approach is tested to be effective by a engineering case of the Chengdu outer ring tunnel.The results show that higher uncertainty of seismic response on face stability should be noticed in areas with intense earthquakes and variation of seismic wave velocity has the most profound influence on tunnel face stability.
