Long-range corrected density functional calculations of chemical reactions: Redetermination of parameter

Abstract

Chemical reaction calculations were carried out using the long-range correction (LC) scheme, which improves long-range exchange effects in density functional theory (DFT) [J. Chem. Phys. 115, 3540 (2001); 120, 8425 (2004)]. A new determination of the LC scheme parameter mu was made by a root mean square fit of the percent error in calculated atomization energies. As a result, the parameter mu was optimized as 0.47, which is higher than the previous one (mu=0.33). Using this new parameter mu, LC-DFT was firstly applied to geometry optimizations of the G2 benchmark set molecules. Consequently, this new LC-DFT gave more accurate bond lengths and bond angles than previous LC-DFT and hybrid B3LYP results. Following this result, the authors calculated reaction barrier height energies of benchmark reaction sets, which have been underestimated in conventional DFT calculations. Calculated results showed that LC-DFT provided much more accurate barrier height energies with errors less than half those of previous LC-DFT and B3LYP studies. To test the general validity of the new LC-DFT, the authors finally calculated reaction enthalpies. As a result, they found that the LC scheme using the new mu clearly improved the accuracy of calculated enthalpies. The authors therefore conclude that the insufficient inclusion of long-range exchange effects is responsible for the underestimation of reaction barriers in DFT calculations and that LC-DFT using the new parameter is a powerful tool for theoretically investigating chemical reactions.