Ab Initio Calculation of Room Temperature Ionic Liquid 1-Ethyl-3-Methyl-Imidazolium Chlorocuprate (Ⅰ)

The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^＋（1-ethyl-3-methyl-imidazolium^＋）, CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM＋^-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2- pairs. Full optimization and frequency analyses of EMIM^＋, CuCl2^-, Cu2Cl3^-, CuC13^-, eight initial EMIM^＋-CuCl2^-, six EMIM^＋-Cu2Cl3^-, and four EMIM^＋-CuCl3^2- geometries have been carried out using Gaussian-94 soft-package at 6-31＋G（d,p） basis set level for hydrogen, carbon, nitrogen, chlorine atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy of EMIM^＋-CuCl2^-, EMIM＋-Cu2Cl3^-, EMIM^＋-CuCl3^2-, single EMIM^＋, CuCl2^-, Cu2Cl3^-, and CuCl3^2- have been comparatively studied. The calculated results showed that EMIM^＋-CuCl2^- pair conformer of lowest energy was five ring parallel to Cl-Cu-Cl with 3.2A distance, EMIM^＋-CuCl3^2- pair conformer of lowest energy was five ring parallel to CuCl3^2-plane with 3.4A distance, and the optimized EMIM^＋-Cu2Cl3^- pair conformer of lowest energy was five ring perpendicular to Cl-Cu-Cl-Cu-Cl plane with 3.0A distance between the terminal Cl atoms and the 5-ring of EMIM^＋. The cohesion between cations and anions is brought about by C-H. C1 hydrogen bonds that are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency. The assigned frequencies were in agreement with the experimental report. The low energy of interaction because of the bulkyasymmetry of EMIM＋ and the charge dispersion of cation and anion leads to the low melting point of the ionic liquids, EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2-. The interaction energy of EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2- is 309.0 kJ/mol, 316.8 kJ/mol, and 320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions was also investigated by single point energy scan.

DFT Calculation of Room Temperature Ionic Liquid 1-Ethyl-3-Methyl-Imidazolium Chlorocuprate (Ⅰ)

The density functional theory （DFT） has been employed to investigate the electronic structures ofEMIM^＋（1-ethyl-3-methylimidazolium＋）, CuCl2^-, Cu2Cl3^- and EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^- pairs. Full optimization and frequency analyses of EMIM^＋, CuCl2^-, Cu2Cl3^-, eight initial EMIM^＋-CuCl2^-, and six initial EMIM^＋-Cu2Cl3^- geometries have been carried out using Gaussian-94 software-package at 6-3 I＋G （d, p） basis set level for hydrogen, carbon, nitrogen, chlorine atoms and the Hay-Wadt effective core potential for copper atoms. The electronic structures of the lowest energy of EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^- pairs, single EMIM^＋, CuCl2^-, and Cu2Cl3^- have been comparatively studied. The calculated results showed that the optimized EMIM^＋-CuCl2^- pair conformer of the lowest energy was five ring moiety parallel to CuCl2^- plane with a distance of around 3.5,A, while EMIM^＋-Cu2Cl3^- pair conformer of the lowest energy was five ring moiety of EMIM^＋ perpendicular to Cu2Cl3^- plane with a distance of around 3.0 ,A between terminal chlorine atoms and 5-ring plane of EMIM^＋. The cohesion between cation and anion is electrostatic interaction and C-H---Cl hydrogen bonds are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum points because of absence of imaginary frequency. The low energy of interaction caused by bulky asymmetry of EMIM^＋, and charge dispersion of cation and anion give rise to low melting point of ionic liquids EMIM^＋-CuCl2^-, and EMIM^＋-Cu2Cl3^- . The interaction energy caused by the distance between cations and anions was investigated by single point energy scan.