We recently reported a study into what causes the dramatic differences between OPBE and PBE for reaction barriers, spin-state energies, hydrogen-bonding and π-π stacking energies.1 It was achieved by smoothly switching from OPBE to PBE at a predefined point P of the reduced density gradient s. By letting the point P run as function of the reduced density gradient s, with values from s=0.1 to s=10, we could determine which part of the exchange functional determines its behavior for the different interactions. Based on the thus obtained results, we created a new exchange functional that showed the good results of OPBE for reaction barriers and spin-state energies, and combined it with the good (H-bonds) and reasonable (π-stacking) results of PBE for weak interactions. In other words, it combined the best of OPBE with the best of PBE. Encouraged by these good results, we have further improved the new exchange functional and fine-tuned its parameters.2 Similar to the switched functional from ref. 1, our new SSB functional2 works well for SN2 barriers (see e.g. ref. 3), spin states and H-bonding interactions. Moreover, by including Grimme's dispersion corrections4,5 (to give our final SSB-D functional) it also works well for π-π stacking interactions.2 In summary, we have constructed a new GGA exchange functional that when combined with the sPBE correlation functional6 gives the correct spin ground-state of iron complexes, and small deviations for SN2 barriers (2.7 kcal⋅mol-1), geometries (0.005 Å), Hbond distances (0.012 Å), weak interactions (S22 set, 0.5 kcal⋅mol-1), and transition-metal ligand distances (0.008 Å).
Skip Nav Destination
Article navigation
10 December 2012
INTERNATIONAL CONFERENCE OF COMPUTATIONAL METHODS IN SCIENCES AND ENGINEERING 2009: (ICCMSE 2009)
29 September–4 October 2009
Rhodes, Greece
Research Article|
December 10 2012
A new DFT functional based on spin-states and SN2 barriers
M. Swart;
M. Swart
Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, E-17071 Girona, Spain and Institució Catalana de Recerca i Estudis Avançats (ICREA), Pg. Lluís Companys 23, E-08,
Spain
Search for other works by this author on:
M. Solà;
M. Solà
Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, E-17071 Girona,
Spain
Search for other works by this author on:
F. M. Bickelhaupt
F. M. Bickelhaupt
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boelelaan 1083, NL-1081 HV Amsterdam,
Netherlands
Search for other works by this author on:
AIP Conf. Proc. 1504, 703–706 (2012)
Citation
M. Swart, M. Solà, F. M. Bickelhaupt; A new DFT functional based on spin-states and SN2 barriers. AIP Conf. Proc. 10 December 2012; 1504 (1): 703–706. https://doi.org/10.1063/1.4771792
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
12
Views
Citing articles via
Inkjet- and flextrail-printing of silicon polymer-based inks for local passivating contacts
Zohreh Kiaee, Andreas Lösel, et al.
Effect of coupling agent type on the self-cleaning and anti-reflective behaviour of advance nanocoating for PV panels application
Taha Tareq Mohammed, Hadia Kadhim Judran, et al.
Design of a 100 MW solar power plant on wetland in Bangladesh
Apu Kowsar, Sumon Chandra Debnath, et al.
Related Content
A new all-round density functional based on spin states and S N 2 barriers
J. Chem. Phys. (September 2009)
Communication: Asymmetrical cation movements through G-quadruplex DNA
J. Chem. Phys. (July 2014)
Analysis of a DNA simulation model through hairpin melting experiments
J. Chem. Phys. (September 2010)
Brownian dynamics simulations of single-stranded DNA hairpins
J. Chem. Phys. (March 2009)