Efficient generation of matrix elements for one-electron spin–orbit operators

Kleinschmidt, Martin; Marian, Christel M.

doi:10.1016/j.chemphys.2004.10.025

Cited by 88 publications

(81 citation statements)

References 26 publications

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“…The obtained energies are in reasonable agreement with previously reported TDDFT and DFT/MRCI results. [17,18,[21][22][23] However, the calculated TDDFT energies of the T 1 and T 2 states now are considerably lower than the respective DFT/MRCI values. As a consequence, the DFT/MRCI method predicts significantly smaller energy distances between the lowest triplet and singlet excited states than does TDDFT.…”

Section: Resultsmentioning

confidence: 89%

“…[17,18,[22][23][24][25] The TDDFT energies of most pp* excited singlet states are characterized by systematic upshifts of % 0.3 eV compared to the DFT/MRCI results. In contrast, the TDDFT singlet transitions of np* type are stabilized by % 0.2 eV in comparison to the respective DFT/MRCI values.…”

Section: Resultsmentioning

confidence: 99%

“…[39] Comparison with earlier work employing a valence triple-zeta basis set with (d,p) polarization functions had shown that the error introduced by utilizing the smaller def-SV(P) basis set is negligible. [17,18] Harmonic vibrational frequencies were calculated numerically at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states with a parallel version of the SNF program. [40] The combined DFT/MRCI method by Grimme and Waletzke was used for single-point energy calculations at the obtained TDDFT equilibrium geometries.…”

Section: Methodsmentioning

confidence: 99%

“…Recently, first results of calculations of SOCMEs have been reported for several porphyrin derivatives. [17,18] Surprisingly, it turned out that SOCMEs of the lowest singlet and triplet states calculated at the T 1 minimum-energy geometries are extremely small (do not exceed 0.01 cm…”

Section: Introductionmentioning

confidence: 98%

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Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

2008

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Extensive time-dependent DFT (TDDFT) and DFT/multireference configuration interaction (MRCI) calculations are performed on the singlet and triplet excited states of free-base porphyrin, with emphasis on intersystem crossing processes. The equilibrium geometries, as well as the vertical and adiabatic excitation energies of the lowest singlet and triplet excited states are determined. Single and double proton-transfer reactions in the first excited singlet state are explored. Harmonic vibrational frequencies are calculated at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states. Furthermore, spin-orbit coupling matrix elements of the lowest singlet and triplet states and their numerical derivatives with respect to nuclear displacements are computed. It is shown that opening of an unprotonated pyrrole ring as well as excited-state single and double proton transfer inside the porphyrin cavity lead to crossings of the potential energy curves of the lowest singlet and triplet excited states. It is also found that displacements along out-of-plane normal modes of the first excited singlet state cause a significant increase of the , , and spin-orbit coupling matrix elements. These phenomena lead to efficient radiationless deactivation of the lowest excited states of free-base porphyrin via intercombination conversion. In particular, the S1-->T1 population transfer is found to proceed at a rate of approximately 10(7) s(-1) in the isolated molecule.

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

2008

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“…The first, one-step, spin-orbit coupling treatment directly diagonalizesĤ in a basis which does not assume spin symmetry. [77][78][79] The second, two-step, state-interaction method expands the eigenstates ofĤ in terms of the spin-pure eigenstates ofĤ SR . 53,54,80,81 The coefficients of expansion may be determined using different methods, such as perturbation theory [82][83][84][85][86] or through diagonalization (state interaction).…”

Section: Theorymentioning

confidence: 99%

A state interaction spin-orbit coupling density matrix renormalization group method

Sayfutyarova

Chan

2016

The Journal of Chemical Physics

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We describe a state interaction spin-orbit (SISO) coupling method using density matrix renormalization group (DMRG) wavefunctions and the spin-orbit mean-field (SOMF) operator. We implement our DMRG-SISO scheme using a spin-adapted algorithm that computes transition density matrices between arbitrary matrix product states. To demonstrate the potential of the DMRG-SISO scheme we present accurate benchmark calculations for the zero-field splitting of the copper and gold atoms, comparing to earlier complete active space self-consistent-field and second-order complete active space perturbation theory results in the same basis. We also compute the effects of spin-orbit coupling on the spin-ladder of the iron-sulfur dimer complex [Fe 2 S 2 (SCH 3 ) 4 ] 3− , determining the splitting of the lowest quartet and sextet states. We find that the magnitude of the zero-field splitting for the higher quartet and sextet states approaches a significant fraction of the Heisenberg exchange parameter. Published by AIP Publishing. [http://dx

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