Anchoring the Potential Energy Surface of the Nitrogen/water Dimer, N2⋯h2o, with Explicitly Correlated Coupled-Cluster Computations
Abstract
Six different stationary points have been identified and characterized on the potential energy surface of N2⋯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-H⋯N interaction and an electronic dissociation energy of 1.22kcalmol-1 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 0.51-0.61kcalmol-1 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. © 2013 Elsevier B.V.
Recommended Citation
T. L. Ellington and G. S. Tschumper, "Anchoring the Potential Energy Surface of the Nitrogen/water Dimer, N2⋯h2o, with Explicitly Correlated Coupled-Cluster Computations," Computational and Theoretical Chemistry, vol. 1021, pp. 109 - 113, Elsevier, Oct 2013.
The definitive version is available at https://doi.org/10.1016/j.comptc.2013.06.035
Department(s)
Chemistry
Keywords and Phrases
CCSD(T) CBS limit; Foreign continuum; Harmonic vibrational frequencies; Nitrogen water dimer potential energy surface
International Standard Serial Number (ISSN)
2210-271X
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 Elsevier, All rights reserved.
Publication Date
01 Oct 2013
Comments
National Science Foundation, Grant 0957317