Secondary hydrogen isotope effects on the structure and stability of cation-pi complexes (cation = Li(+), Na(+), K(+) and pi = acetylene, ethylene, benzene).
Secondary hydrogen isotope effects on the geometries, electronic wave functions and binding energies of cation-pi complexes (cation = Li(+), Na(+), K(+) and pi = acetylene, ethylene, benzene) are investigated with NEO/HF and NEO/MP2 methods. These methods determine both electronic and nuclear wave functions simultaneously. Our results show that an increase of the hydrogen nuclear mass leads to the elongation of the cation-pi bond distance and the decrease in its binding energy. An explanation to this behavior is given in terms of the changes in the pi-molecule electronic structure and electrostatic potential induced by isotopic substitutions.
Moreno
Diego V
DV
Department of Chemistry, Universidad Nacional de Colombia, Av. Cra 30 45-03, Bogotá, Colombia.
González
Sergio A
SA
Reyes
Andrés
A
D000114:Acetylene / Q000737:chemistry; D001554:Benzene / Q000737:chemistry; D004583:Electrons; D005030:Ethylenes / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D007554:Isotopes; D008094:Lithium / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011188:Potassium / Q000737:chemistry; D012964:Sodium / Q000737:chemistry
D005030:Ethylenes; D007554:Isotopes; D009942:Organometallic Compounds; D006859:Hydrogen; C036216:ethylene; D008094:Lithium; D012964:Sodium; D001554:Benzene; D000114:Acetylene; D011188:Potassium