The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates

Powers, Anna; Scribano, Yohann; Lauvergnat, David; Mebe, Elsy; Benoit, David M.; Bačić, Zlatko

Abstract

© 2018 Author(s). We report a theoretical study of the frequency shift (redshift) of the stretching fundamental transition of an H 2 molecule confined inside the small dodecahedral cage of the structure II clathrate hydrate and its dependence on the condensed-phase environment. In order to determine how much the hydrate water molecules beyond the confining small cage contribute to the vibrational frequency shift, quantum five-dimensional (5D) calculat ions of the coupled translation-rotation eigenstates are performed for H 2 in the v=0 and v=1 vibrational states inside spherical clathrate hydrate domains of increasing radius and a growing number of water molecules, ranging from 20 for the isolated small cage to over 1900. In these calculations, both H 2 and the water domains are treated as rigid. The 5D intermolecular potential energy surface (PES) of H 2 inside a hydrate domain is assumed to be pairwise additive. The H 2 -H 2 O pair interaction, represented by the 5D (rigid monomer) PES that depends on the vibrational state of H 2 , v=0 or v=1, is derived from the high-quality ab initio full-dimensional (9D) PES of the H 2 -H 2 O complex [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)]. The H 2 vibrational frequency shift calculated for the largest clathrate domain considered, which mimics the condensed-phase environment, is about 10% larger in magnitude than that obtained by taking into account only the small cage. The calculated splittings of the translational fundamental of H 2 change very little with the domain size, unlike the H 2 j = 1 rotational splittings that decrease significantly as the domain size increases. The changes in both the vibrational frequency shift and the j = 1 rotational splitting due to the condensed-phase effects arise predominantly from the H 2 O molecules in the first three complete hydration shells around H 2 .

Citation

Powers, A., Scribano, Y., Lauvergnat, D., Mebe, E., Benoit, D. M., & Bačić, Z. (2018). The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates. The Journal of chemical physics, 148(14), 144304. https://doi.org/10.1063/1.5024884

• Journal Article Type: Article
• Acceptance Date: Mar 1, 2018
• Online Publication Date: Apr 9, 2018
• Publication Date: Apr 14, 2018
• Deposit Date: May 18, 2018
• Publicly Available Date: May 21, 2018
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 148
• Issue: 14
• Article Number: 144304
• Pages: 144304
• DOI: https://doi.org/10.1063/1.5024884
• Public URL: https://hull-repository.worktribe.com/output/794098
• Publisher URL: https://aip.scitation.org/doi/10.1063/1.5024884
• Contract Date: May 21, 2018