7 research outputs found
Correlated exponential functions in high precision calculations for diatomic molecules
Various properties of the general two-center two-electron integral over the
explicitly correlated exponential function are analyzed for the potential use
in high precision calculations for diatomic molecules. A compact one
dimensional integral representation is found, which is suited for the numerical
evaluation. Together with recurrence relations, it makes possible the
calculation of the two-center two-electron integral with arbitrary powers of
electron distances. Alternative approach via the Taylor series in the
internuclear distance is also investigated. Although numerically slower, it can
be used in cases when recurrences lose stability. Separate analysis is devoted
to molecular integrals with integer powers of interelectronic distances
and the vanishing corresponding nonlinear parameter. Several methods
of their evaluation are proposed.Comment: 26 pages, includes two tables with exemplary calculation
Experimental And Theoretical Investigation Of The Reaction Between Co2 And Carbon Dioxide Binding Organic Liquids
The reaction kinetics of CO2 absorption into new carbon dioxide binding organic liquids (CO(2)BOLs) was comprehensively studied to evaluate their potential for CO2 removal. A stopped-flow apparatus with conductivity detection was used to determine the CO2 absorption kinetics of novel CO(2)BOLs composed of DBN (1,5-diazabicyclo[4.3.0]non-5-ene)/1-propanol and TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene)/1-butanol. A modified termolecular reaction mechanism for the reaction of CO2 with CO(2)BOLs was used to calculate the observed pseudo-first order rate constant k(0) (s(-1)) and second-order reaction rate constant k(2) (m(3)/kmol.s). Experiments were performed by varying organic base (DBN or TBD) weight percentage in alcohol medium for a temperature range of 288-308 K. It was found that k(0) increased with increasing amine concentration and temperature. By comparing using two different CO2BOL systems, it was observed that the TBD/1-butanol system has faster reaction kinetics than the DBN/1-propanol system. Finally, experimental and theoretical activation energies of these CO2BOL systems were obtained and compared. Quantum chemical calculations using spin restricted B3LYP and MP2 methods were utilized to reveal the structural and energetic details of the single-step termolecular reaction mechanism.WoSScopu