Structural Chemistry

, Volume 30, Issue 6, pp 2191–2204 | Cite as

Probing non-covalent interactions of phosphine and arsine derivatives: an energy decomposition analysis using localized molecular orbitals

  • Bilal Ahmad ShiekhEmail author
  • Damanjit Kaur
  • Rajinder Kaur
Original Research


Ab initio (MP2/aug-cc-pVTZ) and density functional theory (DFT) (B3PW91/aug-cc-pVTZ and B3LYP-D3/Def2-TZVPP) analyses have been carried out to characterize the bonding of phosphine and arsine derivatives i.e., M-RH2–HF (M = As or P, R = furan, pyridine, pyrrole, and thiophene) with hydrogen fluoride (HF). Two minima were found on the potential energy surface (PES) for each complex, one in which HF is forming directly an H-bond with pnicogen while the other one in which HF is interacting with the heterocyclic ring in addition to normal H-bond. The latter one is highly stable with MP2/CBS extrapolated binding energies ranging from − 10.67 kcal mol−1 to − 6.33 kcal mol−1. The interaction energies in these complexes follow the order P-PyrHF > P-ThioHF > P-FuHF > P-PyHF > As-PyrHF > As-ThioHF > As-FuHF > As-PyHF. NBO analysis demonstrated that \( {LP}_{As/P}\to {\sigma}_{H-F}^{\ast } \) orbital interaction plays a major role in stabilizing these complexes, and the largest charge is transferred in P-type complexes compared with their As-type analogs. The LMO-EDA pointed out that all the partitioning terms are stabilizing in nature with a dominant role carried out by exchange energy while as the repulsion energy is the only term being destabilizing in nature. Many body interaction analysis in ternary complexes M-RH2–(HF)2, in which the other interaction site of heterocyclic rings (N, O, and S) were used for second H-bonding with another HF molecule, revealed that the second H-bond is destabilizing the pnicogen H-bond and showed negative synergetic effects.


Non-covalent interactions Phosphine and arsine derivatives PES LMO-EDA Cooperation energy 



The authors are thankful to Anuraj Kaur for providing the help needed to complete the work.

Funding information

This work was financially supported by UGC, Govt. of India under UGC-BSR scheme as SRF (Senior Research Fellow) vide notification number, NO.F.25-1/2013-14(BSR)/5-27/2007(BSR).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.

Supplementary material

11224_2019_1328_MOESM1_ESM.doc (73.9 mb)
ESM 1 (DOC 75717 kb)


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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Bilal Ahmad Shiekh
    • 1
    Email author
  • Damanjit Kaur
    • 1
  • Rajinder Kaur
    • 1
  1. 1.Department of Chemistry, UGC Sponsored Centre of Advanced, z Studies-IGuru Nanak Dev UniversityAmritsarIndia

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