A series of novel atomic structure of lowest-energy Fe_(n)P_(13-n)(n=0-13)clusters via density functional theory(DFT)calculations and an unbiased structure search using Crystal structure AnaLYsis by Particle Swarm Opt...A series of novel atomic structure of lowest-energy Fe_(n)P_(13-n)(n=0-13)clusters via density functional theory(DFT)calculations and an unbiased structure search using Crystal structure AnaLYsis by Particle Swarm Optimization(CALYPSO)code.Our research results show that the global minimum geometry structure of neutral Fe_(13-n)P_(n)(n=0-6)clusters tend to form cage structures but the lowest-energy Fe_(13-n)P_(n)(n=7-13)clusters are gradually evolution from a cage structure to a chain shape geometric structure.Their geometric structure should responsible for the raise of binding energy from Fe_7P_(6)to P_(13)clusters rather than chemical components.This is completely different from a linear relation of the binding energy with chemical components in our previous research for Cu_(n)Zr_(13-n)(n=3-10)clusters(J.Mol.Liq.343117603(2021)).Hence,in order to characterize the global chemical stability of target cluster,we proposed a new parameter(jyq=η/χ)that the chemical hardness of isolated cluster is used to be divided by its electronegativity.One of the biggest advantages of this parameter is successful coupling the ability of a resistance to redistribution of electrons and the ability to attract electrons from other system(such as atom,molecular or metallic clusters).Moreover,it is found that the P_(13)cluster shows typical insulator characteristics but the Fe_(12)P_(1)shows typical conductor characteristics,which phenomena can be attributed to the remarkable delocalized and localized electrons in Fe_(12)P_(1)and P_(13),respectively.In terms of nearly-free-electron mode,we also found that the number of electrons on Femi level(N(E_F))are obviously tended to toward a lower value when Fe was replaced gradually with P from Fe_(13)to P_(13),and a non-magnetic can be observed in Fe_(13),Fe_(2)P_(11),Fe_(1)P_(12),and P_(13)that mainly because their perfect symmetrical between spin-up and spin-down of density of states of electrons.展开更多
采用密度泛函理论(Density Function Theory,DFT)中的B3LYP和B3PW 91方法,在LanL2DZ赝势基组水平上对Ptn0,±(n=2~4)团簇的几何构型和稳定性进行了研究,主要从振动频率、能级、解离能3个方面进行了分析.研究表明:铂三聚物的中性、...采用密度泛函理论(Density Function Theory,DFT)中的B3LYP和B3PW 91方法,在LanL2DZ赝势基组水平上对Ptn0,±(n=2~4)团簇的几何构型和稳定性进行了研究,主要从振动频率、能级、解离能3个方面进行了分析.研究表明:铂三聚物的中性、阴离子和阳离子最稳定结构都为等腰三角形;四聚物的中性、阴离子的最稳定结构都是二面体,阳离子则是正四面体结构最稳定.所计算的结果都与实验值相符合.展开更多
With the aid of the molecular orbital DMol3 program,the energetics and electronic structures of several AlnC（n = 2-7） configurations have been searched and calculated by improved minimum energy paths（MEPs） by sett...With the aid of the molecular orbital DMol3 program,the energetics and electronic structures of several AlnC（n = 2-7） configurations have been searched and calculated by improved minimum energy paths（MEPs） by setting ＂imaging product＂.A new high symmetry,supervalence isomer of Al5C cluster,i.e.,D5h-Al5C,at the local minimum in the MEPs is detected.Several parameters,such as binding energy,HOMO-LUMO energy gap,vertical electron detachment energy and electron affinity energy,are calculated to characterize and evaluate the stability of three Al5C configurations,i.e.,D5h-Al5C,Cs-Al5C and C1-Al5C.The results show that the D5h-Al5C cluster is the ground state structure instead of Cs-Al5C.Due to the formation of many central σ bonds after polymerizing for D5h-Al5C,the decrease of the energy for HOMO orbit results in more territory for HOMO electrons of dislocation effect,then the energy difference between HOMO and LUMO is increasing to enhance the stability of molecules to produce such supervalence structure of Al5C cluster.The configuration evolution between D5h-Al5C,Cs-Al5C and C1-Al5C and the synthesis preference in the mode of Al5 ＋ C → Al5C reveals that the Cs-Al5C and C1-Al5C con-figurations are permissive to coexist with D5h-Al5C structure in energetics.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.52263025 and 51871096)the Scientific Research Project of the Education Department of Jiangxi Province,China(Grant Nos.GJJ2202021and GJJ2202011)+3 种基金the Natural Science Foundation of Jiangxi ProvinceChina(Grant Nos.20202BAB204004 and20171BAB216001)the Qinglan Scholars ProgramScientific Research Project(Grant No.22XJSK04)of Nanchang Normal University。
文摘A series of novel atomic structure of lowest-energy Fe_(n)P_(13-n)(n=0-13)clusters via density functional theory(DFT)calculations and an unbiased structure search using Crystal structure AnaLYsis by Particle Swarm Optimization(CALYPSO)code.Our research results show that the global minimum geometry structure of neutral Fe_(13-n)P_(n)(n=0-6)clusters tend to form cage structures but the lowest-energy Fe_(13-n)P_(n)(n=7-13)clusters are gradually evolution from a cage structure to a chain shape geometric structure.Their geometric structure should responsible for the raise of binding energy from Fe_7P_(6)to P_(13)clusters rather than chemical components.This is completely different from a linear relation of the binding energy with chemical components in our previous research for Cu_(n)Zr_(13-n)(n=3-10)clusters(J.Mol.Liq.343117603(2021)).Hence,in order to characterize the global chemical stability of target cluster,we proposed a new parameter(jyq=η/χ)that the chemical hardness of isolated cluster is used to be divided by its electronegativity.One of the biggest advantages of this parameter is successful coupling the ability of a resistance to redistribution of electrons and the ability to attract electrons from other system(such as atom,molecular or metallic clusters).Moreover,it is found that the P_(13)cluster shows typical insulator characteristics but the Fe_(12)P_(1)shows typical conductor characteristics,which phenomena can be attributed to the remarkable delocalized and localized electrons in Fe_(12)P_(1)and P_(13),respectively.In terms of nearly-free-electron mode,we also found that the number of electrons on Femi level(N(E_F))are obviously tended to toward a lower value when Fe was replaced gradually with P from Fe_(13)to P_(13),and a non-magnetic can be observed in Fe_(13),Fe_(2)P_(11),Fe_(1)P_(12),and P_(13)that mainly because their perfect symmetrical between spin-up and spin-down of density of states of electrons.
文摘采用密度泛函理论(Density Function Theory,DFT)中的B3LYP和B3PW 91方法,在LanL2DZ赝势基组水平上对Ptn0,±(n=2~4)团簇的几何构型和稳定性进行了研究,主要从振动频率、能级、解离能3个方面进行了分析.研究表明:铂三聚物的中性、阴离子和阳离子最稳定结构都为等腰三角形;四聚物的中性、阴离子的最稳定结构都是二面体,阳离子则是正四面体结构最稳定.所计算的结果都与实验值相符合.
基金Supported by the National Natural Science Foundation of China (No.50771044)the Doctor Start up Foundation of Nanchang Hangkong University (EA201001034)Youth Science Foundation of Jiangxi Educational Committee (GJJ11157)
文摘With the aid of the molecular orbital DMol3 program,the energetics and electronic structures of several AlnC（n = 2-7） configurations have been searched and calculated by improved minimum energy paths（MEPs） by setting ＂imaging product＂.A new high symmetry,supervalence isomer of Al5C cluster,i.e.,D5h-Al5C,at the local minimum in the MEPs is detected.Several parameters,such as binding energy,HOMO-LUMO energy gap,vertical electron detachment energy and electron affinity energy,are calculated to characterize and evaluate the stability of three Al5C configurations,i.e.,D5h-Al5C,Cs-Al5C and C1-Al5C.The results show that the D5h-Al5C cluster is the ground state structure instead of Cs-Al5C.Due to the formation of many central σ bonds after polymerizing for D5h-Al5C,the decrease of the energy for HOMO orbit results in more territory for HOMO electrons of dislocation effect,then the energy difference between HOMO and LUMO is increasing to enhance the stability of molecules to produce such supervalence structure of Al5C cluster.The configuration evolution between D5h-Al5C,Cs-Al5C and C1-Al5C and the synthesis preference in the mode of Al5 ＋ C → Al5C reveals that the Cs-Al5C and C1-Al5C con-figurations are permissive to coexist with D5h-Al5C structure in energetics.
