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.
