Analysis of the intermolecular interaction between CH(3)OCH(3), CF(3)OCH(3), CF(3)OCF(3), and CH(4): high level ab initio calculations.
The intermolecular interaction energies of the CH(3)OCH(3)-CH(4), CF(3)OCH(3)-CH(4), and CF(3)OCF(3)-CH(4) systems were calculated by ab initio molecular orbital method with the electron correlation correction at the second order Møller-Plesset perturbation (MP2) method. The interaction energies of 10 orientations of complexes were calculated for each system. The largest interaction energies calculated for the three systems are -1.06, -0.70, and -0.80 kcal/mol, respectively. The inclusion of electron correlation increases the attraction significantly. It gains the attraction -1.47, -1.19, and -1.27 kcal/mol, respectively. The dispersion interaction is found to be the major source of the attraction in these systems. In the CH(3)OCH(3)-CH(4) system, the electrostatic interaction (-0.34 kcal/mol) increases the attraction substantially, while the electrostatic energies in the other systems are not large. Fluorine substitution of the ether decreases the electrostatic interaction, and therefore, decreases the attraction. In addition the orientation dependence of the interaction energy is decreased by the substitution.
Urata
Shingo
S
Research Institute of Innovative Technology for the Earth, AIST, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan. shingo@agc.co.jp
Tsuzuki
Seiji
S
Mikami
Masuhiro
M
Takada
Akira
A
Uchimaru
Tadafumi
T
Sekiya
Akira
A