Restricted open-shell Kohn–Sham theory for π–π* transitions. II. Simulation of photochemical reactions

Nonnenberg, Christel; Grimm, Stephan; Frank, Irmgard

doi:10.1063/1.1623743

Cited by 34 publications

(23 citation statements)

References 56 publications

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“…This feature may be exploited to maintain the conservation of orbital symmetry. 8 In contrast to adiabatic approaches such as timedependent DFT ͑TDDFT͒ and complete-active-space selfconsistent field ͑CASSCF͒, the single-configuration method ROKS behaves diabatically ͑see Fig. 1͒.…”

Section: Introductionmentioning

confidence: 98%

“…With restricted open-shell KohnSham ͑ROKS͒ theory 6,7 this approach has been extended to the simulation of photoreactions. [8][9][10][11] In this field on-the-fly simulations are particularly useful because the motion of the nuclei can be modeled for all degrees of freedom. The dynamics of the relaxation from the Franck-Condon regioncorresponding to an excited state system with approximately ground state geometry-to the minimum of the excited state can be simulated.…”

Section: Introductionmentioning

confidence: 99%

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Restricted open-shell Kohn-Sham theory: Simulation of the pyrrole photodissociation

Frank

Damianos

2007

The Journal of Chemical Physics

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The authors study the photodissociation reactions of pyrrole and N-methylpyrrole using first-principles molecular dynamics. The first excited state is described with restricted open-shell Kohn-Sham theory. They find a small barrier in the excited state potential energy surface. The possibility of energy redistribution near the Franck-Condon region leads to two different reaction channels in on-the-fly simulations on a single diabatic potential energy surface. The results are discussed in comparison with previous ab initio calculations and with experiments.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Restricted open-shell Kohn-Sham theory: Simulation of the pyrrole photodissociation

Frank

Damianos

2007

The Journal of Chemical Physics

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“…Cyclohexa-1,3-diene (CHD) is one of the most thoroughly studied molecules in time resolved photoexcitation experiments [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] and ab initio computations 9,15,[17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] and is the subject of two recent reviews. 32,33 The large interest originally stems from CHD being the prototype for a pericyclic reaction used to explain the Woodward-Hoffmann rules.…”

Section: Introductionmentioning

confidence: 99%

Cyclohexadiene Revisited: A Time-Resolved Photoelectron Spectroscopy and ab Initio Study

et al. 2016

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We have reinvestigated the excited state dynamics of cyclohexa-1,3-diene (CHD) with time-resolved photoelectron spectroscopy and fewest switches surface hopping molecular dynamics based on linear response time-dependent density functional theory after excitation to the lowest lying ππ* (1B) state. The combination of both theory and experiment revealed several new results: First, the dynamics progress on one single excited state surface. After an incubation time of 35 ± 10 fs on the excited state, the dynamics proceed to the ground state in an additional 60 ± 10 fs, either via a conrotatory ring-opening to hexatriene or back to the CHD ground state. Moreover, ring-opening predominantly occurs when the wavepacket crosses the region of strong nonadiabatic coupling with a positive velocity in the bond alternation coordinate. After 100 fs, trajectories remaining in the excited state must return to the CHD ground state. This extra time delay induces a revival of the photoelectron signal and is an experimental confirmation of the previously formulated model of two parallel reaction channels with distinct time constants. Finally, our simulations suggest that after the initially formed cis-Z-cis HT rotamer the trans-Z-trans isomer is formed, before the thermodynamical equilibrium of three possible rotamers is reached after 1 ps.

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“…This is indicated by the superscript ' '(ss).' ' The multiplet-DFT scheme of Daul [117,118] and the restricted open-shell KS (ROKS) scheme [119][120][121][122][123][124] as well as related approaches [125,126] proceed along these lines, but usually include additional ideas originating from Hartree-Fock theory. [127,128] It appears that if applied in a spin-restricted formalism, all available approximate exchange-correlation functionals have to be understood as approximations to E ðssÞ xc [q, Q] and not as approximations to E xc [q, Q].…”

Section: Spin States In Ks-dftmentioning

confidence: 99%

“…u i ðrÞ ¼ i u i ðrÞ: (124) For the resulting single Slater determinant, the electron density is given by…”

Section: Relativistic Current-dftmentioning

confidence: 99%

Spin in density‐functional theory

Jacob¹,

Reiher²

2012

Int J of Quantum Chemistry

215

224

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The accurate description of open-shell molecules, in particular of transition metal complexes and clusters, is still an important challenge for quantum chemistry. Although density-functional theory (DFT) is widely applied in this area, the sometimes severe limitations of its currently available approximate realizations often preclude its application as a predictive theory. Here, we review the foundations of DFT applied to open-shell systems, both within the nonrelativistic and the relativistic framework. In particular, we provide an in-depth discussion of the exact theory, with a focus on the role of the spin density and possibilities for targeting specific spin states. It turns out that different options exist for setting up Kohn-Sham DFT schemes for open-shell systems, which imply different definitions of the exchangecorrelation energy functional and lead to different exact conditions on this functional. Finally, we suggest possible directions for future developments.

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Restricted open-shell Kohn–Sham theory for π–π* transitions. II. Simulation of photochemical reactions

Cited by 34 publications

References 56 publications

Restricted open-shell Kohn-Sham theory: Simulation of the pyrrole photodissociation

Restricted open-shell Kohn-Sham theory: Simulation of the pyrrole photodissociation

Cyclohexadiene Revisited: A Time-Resolved Photoelectron Spectroscopy and ab Initio Study

Spin in density‐functional theory

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