Article

Optimizing conical intersections by spin-flip density functional theory: application to ethylene.

Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA
The Journal of Physical Chemistry A (Impact Factor: 2.77). 11/2009; 113(46):12749-53. DOI: 10.1021/jp908032x
Source: PubMed

ABSTRACT Conical intersections (CIs) of ethylene have been successfully determined using spin-flip density functional theory (SFDFT) combined with a penalty-constrained optimization method. We present in detail three structures, twisted-pyramidalized, hydrogen-migrated, and ethylidene CIs. In contrast to the linear response time-dependent density functional theory, which predicts a purely twisted geometry without pyramidalization as the S(1) global minimum, SFDFT gives a pyramidalized structure. Therefore, this is the first correct optimization of CI points of twisted ethylene by the DFT method. The calculated energies and geometries are in good agreement with those obtained by the multireference configuration interaction (MR-CI) method and the multistate formulation of second-order multireference perturbation theory (MS-CASPT2).

0 Bookmarks
 · 
108 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: Time-dependent density functional theory (TDDFT) holds great promise for studying photochemistry because of its affordable cost for large systems and for repeated calculations as required for direct dynamics. The chief obstacle is uncertain accuracy. There have been many validation studies, but there are also many formulations, and there have been few studies where several formulations were applied systematically to the same problems. Another issue, when TDDFT is applied with only a single exchange-correlation functional, is that errors in the functional may mask successes or failures of the formulation. Here, to try to sort out some of the issues, we apply eight formulations of adiabatic TDDFT to the first valence excitations of ten molecules with 18 density functionals of diverse types. The formulations examined are linear response from the ground state (LR-TDDFT), linear response from the ground state with the Tamm-Dancoff approximation (TDDFT-TDA), the original collinear spin-flip approximation with the Tamm-Dancoff (TD) approximation (SF1-TDDFT-TDA), the original noncollinear spin-flip approximation with the TDA approximation (SF1-NC-TDDFT-TDA), combined self-consistent-field (SCF) and collinear spin-flip calculations in the original spin-projected form (SF2-TDDFT-TDA) or non-spin-projected (NSF2-TDDFT-TDA), and combined SCF and noncollinear spin-flip calculations (SF2-NC-TDDFT-TDA and NSF2-NC-TDDFT-TDA). Comparing LR-TDDFT to TDDFT-TDA, we observed that the excitation energy is raised by the TDA; this brings the excitation energies underestimated by full linear response closer to experiment, but sometimes it makes the results worse. For ethylene and butadiene, the excitation energies are underestimated by LR-TDDFT, and the error becomes smaller making the TDA. Neither SF1-TDDFT-TDA nor SF2-TDDFT-TDA provides a lower mean unsigned error than LR-TDDFT or TDDFT-TDA. The comparison between collinear and noncollinear kernels shows that the noncollinear kernel drastically reduces the spin contamination in the systems considered here, and it makes the results more accurate than collinear spin-flip TDDFT for functionals with a low percentage of Hartree-Fock exchange and sometimes for functionals with a higher percentage of Hartree-Fock exchange, but it yields less accurate results than ground-state TDDFT.
    The Journal of Chemical Physics 04/2013; 138(13):134111. · 3.12 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: A number of commonly available density functionals have been tested for their ability to describe the energetics and the geometry at conical intersections in connection with the spin-restricted ensemble referenced Kohn-Sham (REKS) method. The minimum energy conical intersections have been optimized for several molecular systems, which are widely used as paradigmatic models of photochemical rearrangements and models of biological chromophores. The results of the calculations are analyzed using the sign-change theorem of Longuet-Higgins and a method of elementary reaction coordinates of Haas et al. The latter approach helps to elucidate the differences between the geometries at conical intersections as predicted by the multireference wave function ab initio methods and by the density functional methods. Overall, the BH&HLYP density functional yields the best results for the conical intersection geometries and energetics.
    Journal of Chemical Theory and Computation 10/2013; 9(10):4526-4541. · 5.39 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: This extensive theoretical study employed the spin-flip density functional theory (SFDFT) method to investigate the photoisomerization of 11-cis-retinal protonated Schiff base (PSB11) and its minimal model tZt-penta-3,5-dieniminium cation (PSB3). Our calculated results indicate that SFDFT can perform very well in describing the ground- and excited-state geometries of PSB3 and PSB11. We located the conical intersection (CI) point and constructed the photoisomerization reaction path of PSB3 and PSB11 by using the SFDFT method. To further verify the SFDFT results, we computed the energy profiles along the constructed linearly interpolated internal coordinate (LIIC) pathways by using high-level theoretical methods, such as the EOM-CCSD, CR-EOM-CCSD(T), CASPT2, NEVPT2, and XMCQDPT2 methods. The SFDFT method predicts that the photoisomerization of PSB3 is barrierless, in accordance with previous complete-active-space self-consistent-field (CASSCF) results. However, an energy barrier is predicted along the LIIC pathways of PSB11. This finding is different from previous CASSCF results and may indicate that the photoisomerization of PSB11 in gas phase is similar to that in solution. However, the higher spin contamination of the SFDFT method in the vicinity of the CI point caused the located CI geometry to deviate from that of the real CI. In addition, the LIIC pathways are only approximations to the minimum energy path (MEP). Thus, further experimental and theoretical studies are needed to verify the existence of an energy barrier along the photoisomerization reaction path of PSB11 in gas phase. © 2013 Wiley Periodicals, Inc.
    Journal of Computational Chemistry 11/2013; · 3.84 Impact Factor