Salient signature of van der Waals interactions

被引:10
|
作者
Via-Nadal, Mireia [1 ,2 ]
Rodriguez-Mayorga, Mauricio [1 ,2 ,3 ,4 ]
Matito, Eduard [1 ,2 ,5 ]
机构
[1] UPV, EHU, Kimika Fak, Pk 1072, Donostia San Sebastian 20080, Euskadi, Spain
[2] Donostia Int Phys Ctr DIPC, Pk 1072, Donostia San Sebastian 20080, Euskadi, Spain
[3] Univ Girona, IQCC, Girona 17071, Catalonia, Spain
[4] Univ Girona, Dept Quim, Girona 17071, Catalonia, Spain
[5] Basque Fdn Sci, IKERBASQUE, Bilbao 48011, Euskadi, Spain
关键词
DENSITY-FUNCTIONAL THEORY; INTRACULE; FORCES;
D O I
10.1103/PhysRevA.96.050501
中图分类号
O43 [光学];
学科分类号
070207 ; 0803 ;
摘要
van der Waals interactions govern the physics of a plethora of molecular structures. It is well known that the leading term in the distance-based London expansion of the van der Waals energy for atomic and molecular dimers decays as 1/R-6, where R is the dimer distance. Using perturbation theory, we find the leading term in the distance-based expansion of the intracule pair density at the interatomic distance. Our results unveil a universal 1/R-3 decay, which is less prone to numerical errors than the 1/R-6 dependency, and it is confirmed numerically in H-2 and He-2 molecules. This signature of van der Waals interactions can be directly used in the construction of approximate pair density and energy functionals including vdW corrections.
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页数:3
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