Projects per year
Abstract
The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper-CO2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate)2 and dicopper Cu2(formate)4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO2, even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller-Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.
Original language | English (US) |
---|---|
Pages (from-to) | 15135-15144 |
Number of pages | 10 |
Journal | Journal of Physical Chemistry C |
Volume | 121 |
Issue number | 28 |
DOIs | |
State | Published - Jul 20 2017 |
Bibliographical note
Publisher Copyright:© 2017 American Chemical Society.
Fingerprint
Dive into the research topics of 'Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks'. Together they form a unique fingerprint.Projects
- 1 Finished
-
Energy Frontier Research Center For Inorganometallic Catalyst Design (DE-SC0012702)
Gagliardi, L., Cramer, C., Lu, C. C., Penn, L., Stein, A. & Truhlar, D. G.
U.S. DEPARTMENT OF ENERGY (USDOE)
8/1/14 → 7/31/18
Project: Research project