| Autor: |
Patkar D; Department of Chemistry, Dr. Harisingh Gour Vishwavidyalaya, (A Central University), Sagar, 470003, India., Ahirwar MB; Department of Chemistry, Dr. Harisingh Gour Vishwavidyalaya, (A Central University), Sagar, 470003, India., Gadre SR; Department of Scientific Computing, Modelling and Simulation, Savitribai Phule Pune University, Pune, 411 007, India., Deshmukh MM; Department of Chemistry, Dr. Harisingh Gour Vishwavidyalaya, (A Central University), Sagar, 470003, India. |
| Abstrakt: |
In this work, our recently proposed molecular tailoring approach (MTA)-based method is employed for the evaluation of individual hydrogen-bond (HB) energies in linear (L) and cyclic (C) hydrogen fluoride clusters, (HF) n ( n = 3 to 8). The estimated individual HB energies calculated at the MP2(full)/aug-cc-pVTZ level for the L-(HF) n are between 6.2 to 9.5 kcal/mol and those in the C-(HF) n lie between 7.9 to 11.4 kcal/mol. The zero-point energy corrections and basis set superposition corrections are found to be very small (less than 0.6 and 1.2 kcal/mol, respectively). The cooperativity contribution toward individual HBs is seen to fall between 1.0 to 4.8 kcal/mol and 3.2 to 6.9 kcal/mol for linear and cyclic clusters, respectively. Interestingly, the HB energies in dimers, cleaved from these clusters, lie in a narrow range (4.4 to 5.2 kcal/mol) suggesting that the large HB strength in (HF) n clusters is mainly due to the large cooperativity contribution, especially for n ≥ 5 (50 to 62% of the HBs energy). Furthermore, the HB energies in these clusters show a good qualitative correlation with geometrical parameters (H···F distance and F-H···F angles), stretching frequencies of F-H bonds, and electron density values at the (3, -1) bond critical points. |
