Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc...Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc-tion with the domain-based local pair natural orbital(DLPNO)method,has been applied to assess the average binding energies(ABEs)of large benzene clus-ters,specifically(C6H6)13,at the coupled cluster singles and doubles with perturbative triples correction[CCSD(T)]level and the complete basis set(CBS)limit.Utilizing GEBF-DLPNO-CCSD(T)/CBS ABEs as benchmarks,various DFT functionals were evaluated.It was found that several functionals with empirical dispersion correction,including M06-2X-D3,B3LYP-D3(BJ),and PBE-D3(BJ),provide accurate descriptions of the ABEs for(C6H6)13 clusters.Additionally,the M06-2X-D3 functional was used to calculate the ABEs and relative stabili-ties of(C6H6)n clusters for n=11,12,13,14,and 15 revealing that the(C6H6)13 cluster ex-hibits the highest relative stability.These findings align with experimental evidence suggest-ing that n=13 is one of the magic numbers for benzene clusters(C6H6)n,with n≤30.展开更多
The traditional separation of bicyclic and tricyclic aromatics from coal tar involves complicated multi-steps and consumes significantly more energy.Previous work accomplished the separation between anthracene-phenant...The traditional separation of bicyclic and tricyclic aromatics from coal tar involves complicated multi-steps and consumes significantly more energy.Previous work accomplished the separation between anthracene-phenanthrene isomers using electrostatic interaction,but for the separation between bicyclic and tricyclic aromatics,electrostatic interactions are difficult to produce a recognizable effect.Naphthalene-based solvents,named as naphthaleneacetamide,naphthaleneethanol,naphthalenemethanol,naphthol,naphthylacetic acid,naphthylacetonitrile,and naphthylamine,respectively,were used for the efficient separation of naphthalene and phenanthrene via dispersion interaction.Results showed that the pre-studied structural parameters are the key factors in selecting an efficient solvent.And the substituents on the intermolecular interactions involved in the separation processes had an important impact,which were evaluated.Naphthalenemethanol exhibited a superior performance with a purity of 96.3 wt%naphthalene products because its electron-donating substituent enables the selective recognition of naphthalene via the dispersion interaction.The used naphthalene-based solvents can be regenerated and recycled via back extraction with a purity of over 90 wt%naphthalene products,suggesting solvent structural stability during the regeneration processes.Notably,the naphthalene-based solvents also demonstrated better separation performance for polycyclic aromatics from coal tar with a purity of over 80 wt%for bicyclic aromatics.This study would enhance the utilization of coal tar as a valuable source of polycyclic aromatics besides broadening the knowledge for applying non-bonded interaction in the separation of polycyclic aromatics technologies.展开更多
基金supported by the National Key R&D Program of China(No.2023YFB3712504)the National Natural Science Foundation of China(Nos.22273038,22073043,and 22033004)。
文摘Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc-tion with the domain-based local pair natural orbital(DLPNO)method,has been applied to assess the average binding energies(ABEs)of large benzene clus-ters,specifically(C6H6)13,at the coupled cluster singles and doubles with perturbative triples correction[CCSD(T)]level and the complete basis set(CBS)limit.Utilizing GEBF-DLPNO-CCSD(T)/CBS ABEs as benchmarks,various DFT functionals were evaluated.It was found that several functionals with empirical dispersion correction,including M06-2X-D3,B3LYP-D3(BJ),and PBE-D3(BJ),provide accurate descriptions of the ABEs for(C6H6)13 clusters.Additionally,the M06-2X-D3 functional was used to calculate the ABEs and relative stabili-ties of(C6H6)n clusters for n=11,12,13,14,and 15 revealing that the(C6H6)13 cluster ex-hibits the highest relative stability.These findings align with experimental evidence suggest-ing that n=13 is one of the magic numbers for benzene clusters(C6H6)n,with n≤30.
基金financial support provided by the National Natural Science Foundation of China(Grant No.22038008)the China Shenhua Coal-to-Liquids Chemical Co.,Ltd.Science and Technology Innovation Project(Grant No.MZYHG-2021-01).
文摘The traditional separation of bicyclic and tricyclic aromatics from coal tar involves complicated multi-steps and consumes significantly more energy.Previous work accomplished the separation between anthracene-phenanthrene isomers using electrostatic interaction,but for the separation between bicyclic and tricyclic aromatics,electrostatic interactions are difficult to produce a recognizable effect.Naphthalene-based solvents,named as naphthaleneacetamide,naphthaleneethanol,naphthalenemethanol,naphthol,naphthylacetic acid,naphthylacetonitrile,and naphthylamine,respectively,were used for the efficient separation of naphthalene and phenanthrene via dispersion interaction.Results showed that the pre-studied structural parameters are the key factors in selecting an efficient solvent.And the substituents on the intermolecular interactions involved in the separation processes had an important impact,which were evaluated.Naphthalenemethanol exhibited a superior performance with a purity of 96.3 wt%naphthalene products because its electron-donating substituent enables the selective recognition of naphthalene via the dispersion interaction.The used naphthalene-based solvents can be regenerated and recycled via back extraction with a purity of over 90 wt%naphthalene products,suggesting solvent structural stability during the regeneration processes.Notably,the naphthalene-based solvents also demonstrated better separation performance for polycyclic aromatics from coal tar with a purity of over 80 wt%for bicyclic aromatics.This study would enhance the utilization of coal tar as a valuable source of polycyclic aromatics besides broadening the knowledge for applying non-bonded interaction in the separation of polycyclic aromatics technologies.
