| Full text | |
| Author(s): |
Total Authors: 3
|
| Affiliation: | [1] Univ Sao Paulo, Inst Phys, Sao Paulo - Brazil
[2] Univ Fed Amazonas, Dept Phys, BR-69077000 Manaus, Amazonas - Brazil
[3] Univ Sao Paulo, Inst Chem, Sao Paulo - Brazil
Total Affiliations: 3
|
| Document type: | Journal article |
| Source: | Molecular Physics; v. 117, n. 6, p. 693-704, MAR 19 2019. |
| Web of Science Citations: | 0 |
| Abstract | |
The indirect nuclear spin-spin coupling constants of homogeneous hydrogen-bonded HCN clusters are compared with those of inhomogeneous HCN clusters where one of the terminal HCN molecules is substituted by its isomer HNC and by LiCN. Both the intra- and intermolecular (across the hydrogen bond) coupling constants are calculated for the linear form of the clusters containing up to three molecular monomers using different hybrid DFT functionals. The geometry of the monomers and clusters is optimised at the B3LYP/6-311++G(d,p) level. The effect of substitution by the ionic compound LiCN on the coupling constants of HCN is found to be more pronounced than that by HNC. The Ramsey parameters that form the total spin-spin coupling constants are also analysed individually. Among the four Ramsey parameters, the Fermi Contact term is found to be the dominant contributor to the total coupling constants in most cases. The presence of LiCN in the cluster tends to decrease the intramolecular Fermi Contact values, while HNC increases the same in all dimers and trimers. The contributions of localised molecular orbitals have been analysed for the HCN-HNC cluster to obtain some additional insight about the SSCC transmission mechanism along the coupling pathway. {[}GRAPHICS] . (AU) | |
| FAPESP's process: | 17/17750-3 - Solvent Effect in NMR Parameters by ab initio Molecular Dynamics |
| Grantee: | Lucas Colucci Ducati |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 15/08541-6 - Nuclear magnetic resonance spectroscopy: beyond molecular structure assignment |
| Grantee: | Claudio Francisco Tormena |
| Support Opportunities: | Research Projects - Thematic Grants |