Computational tools on top of first principle calculations have played an indispensable role in revealing the molecular details,thermodynamics,and kinetics in catalytic reactions.Here we proposed a highly efficient dy...Computational tools on top of first principle calculations have played an indispensable role in revealing the molecular details,thermodynamics,and kinetics in catalytic reactions.Here we proposed a highly efficient dynamic strategy for the calculation of thermodynamic and kinetic properties in heterogeneous catalysis on the basis of efficient potential energy surface(PES)and MD simulations.Taking CO adsorbate on Ru(0001)surface as the illustrative model system,we demonstrated the PES-based MD can efficiently generate reliable two-dimensional potential-of-mean-force(PMF)surfaces in a wide range of temperatures,and thus temperature-dependent thermodynamic properties can be obtained in a comprehensive investigation on the whole PMF surface.Moreover,MD offers an effective way to describe the surface kinetics such as adsorbate on-surface movement,which goes beyond the most popular static approach based on free energy barrier and transition state theory(TST).We further revealed that the dynamic strategy significantly improves the predictions of both thermodynamic and kinetic properties as compared to the popular ideal statistic mechanics approaches such as harmonic analysis and TST.It is expected that this accurate yet efficient dynamic strategy can be powerful in understanding mechanisms and reactivity of a catalytic surface system,and further guides the rational design of heterogeneous catalysts.展开更多
An accurate description of catalytic selectivity poses an enormous challenge for theoretical simulations.Due to the absence of a well-defined benchmark set on the catalytic selectivity,the performance of even the wide...An accurate description of catalytic selectivity poses an enormous challenge for theoretical simulations.Due to the absence of a well-defined benchmark set on the catalytic selectivity,the performance of even the widely used density functional approximations(DFAs)is yet to be validated.This work reports a test set based on the selective hydrogenation ofα,β-unsaturated aldehydes catalyzed by ruthenium(Ru)hydride complexes.Special attention is paid to benchmark the regioselectivity of aldehydes to either unsaturated alcohols or saturated aldehydes.Accurate reference data were calculated by the massive parallel implementation of the coupled-cluster single,double,and perturbative triple excitations[CCSD(T)]approach,based completely on set limits.Furthermore,we performed the microkinetic simulation based on the CCSD(T)energy profiles,serving the most direct criteria for the performance of DFAs on catalytic selectivity of hydrogenation reactions.Using this test set,we uncovered the intrinsic difficulty of semilocal and hybrid functionals for such a purpose.In the context of the XYG3-type double hybrid(xDH)framework,we showed that this particular challenge could be addressed by the top rung functionals only when the many-body nondynamic correlation effect was accounted for adequately.A recently proposed xDH,namely scsRPA,showed unprecedented accuracy with only 5%error on average.The predicted kinetic selectivity by scsRPA is in close agreement with the reference value,revealing a unique versatility of the top rung DFAs for a reliable description of catalytic selectivity of hydrogenation reactions.展开更多
基金financially supported by Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR109)the National Natural Science Foundation of China(Nos.21973094,22173104,22173105)the Opening Project of PCOSS of Xiamen University(No.201908)。
文摘Computational tools on top of first principle calculations have played an indispensable role in revealing the molecular details,thermodynamics,and kinetics in catalytic reactions.Here we proposed a highly efficient dynamic strategy for the calculation of thermodynamic and kinetic properties in heterogeneous catalysis on the basis of efficient potential energy surface(PES)and MD simulations.Taking CO adsorbate on Ru(0001)surface as the illustrative model system,we demonstrated the PES-based MD can efficiently generate reliable two-dimensional potential-of-mean-force(PMF)surfaces in a wide range of temperatures,and thus temperature-dependent thermodynamic properties can be obtained in a comprehensive investigation on the whole PMF surface.Moreover,MD offers an effective way to describe the surface kinetics such as adsorbate on-surface movement,which goes beyond the most popular static approach based on free energy barrier and transition state theory(TST).We further revealed that the dynamic strategy significantly improves the predictions of both thermodynamic and kinetic properties as compared to the popular ideal statistic mechanics approaches such as harmonic analysis and TST.It is expected that this accurate yet efficient dynamic strategy can be powerful in understanding mechanisms and reactivity of a catalytic surface system,and further guides the rational design of heterogeneous catalysts.
基金supported by the National Natural Science Foundation of China(nos.21688102,21973015,21973094,and 91427301)the Science Challenge Project(no.TZ2018004)+1 种基金an innovative research team of high-level local universities in Shanghai,and a key laboratory program of the Education Commission of Shanghai Municipality(no.ZDSYS14005)the Natural Science Foundation of Fujian Province(no.2019J01131).
文摘An accurate description of catalytic selectivity poses an enormous challenge for theoretical simulations.Due to the absence of a well-defined benchmark set on the catalytic selectivity,the performance of even the widely used density functional approximations(DFAs)is yet to be validated.This work reports a test set based on the selective hydrogenation ofα,β-unsaturated aldehydes catalyzed by ruthenium(Ru)hydride complexes.Special attention is paid to benchmark the regioselectivity of aldehydes to either unsaturated alcohols or saturated aldehydes.Accurate reference data were calculated by the massive parallel implementation of the coupled-cluster single,double,and perturbative triple excitations[CCSD(T)]approach,based completely on set limits.Furthermore,we performed the microkinetic simulation based on the CCSD(T)energy profiles,serving the most direct criteria for the performance of DFAs on catalytic selectivity of hydrogenation reactions.Using this test set,we uncovered the intrinsic difficulty of semilocal and hybrid functionals for such a purpose.In the context of the XYG3-type double hybrid(xDH)framework,we showed that this particular challenge could be addressed by the top rung functionals only when the many-body nondynamic correlation effect was accounted for adequately.A recently proposed xDH,namely scsRPA,showed unprecedented accuracy with only 5%error on average.The predicted kinetic selectivity by scsRPA is in close agreement with the reference value,revealing a unique versatility of the top rung DFAs for a reliable description of catalytic selectivity of hydrogenation reactions.
