کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5393927 | 1505604 | 2013 | 5 صفحه PDF | دانلود رایگان |
- Energetics of nitrogen/water dimer characterized at the CCSD(T) complete basis set (CBS) limit.
- Three transition states have been identified that lie 0.51-0.61 kcal molâ1 above the global minimum at the CCSD(T) CBS limit.
- Resolved discrepancy over identity of global minimum with CCSD(T) computations and basis sets as large as aug-cc-pVQZ.
- IR activity of OH stretching vibrations increases substantially upon dimerization within double harmonic approximation.
Six different stationary points have been identified and characterized on the potential energy surface of N2â¯H2O (i.e., the non-covalent dimer formed between nitrogen and water). Optimized geometries and harmonic vibrational frequencies have been computed using the MP2 and CCSD(T) ab initio electronic structure methods in conjunction with a series of correlation consistent basis sets as large as aug-cc-pVQZ. In addition, explicitly correlated CCSD(T)-F12 single point energy computations in conjunction with basis sets as large as aug-cc-pV5Z have been used to estimate the relative energetics at the complete basis set (CBS) limit. Only one configuration corresponds to a minimum, a Cs structure with an O-Hâ¯N interaction and an electronic dissociation energy of 1.22 kcal molâ1 at the CCSD(T) CBS limit. CCSD(T) harmonic vibrational frequency computations indicate that the IR intensities of the OH stretching modes increase substantially when the dimer forms. Three transition states lie 0.51-0.61 kcal molâ1 above the global minimum at the CCSD(T) CBS limit, which indicates that the barriers associated with rearrangement pathways are comparable to those for (H2O)2.
A single minimum on the nitrogen/water dimer potential energy surface has been identified with an electronic dissociation energy of 1.22 kcal molâ1 at the CCSD(T) complete basis set limit.
Journal: Computational and Theoretical Chemistry - Volume 1021, 1 October 2013, Pages 109-113