Nonadiabatic ab initio molecular dynamics using linear-response time-dependent density functional theory

Curchod, Basile F. E.; Penfold, Thomas J.; Röthlisberger, Ursula; Tavernelli, Ivano

doi:10.2478/s11534-013-0321-2

Cited by 8 publications

(12 citation statements)

References 43 publications

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“…38is analytic and ultrafast owing to the STO representation of the SOMO. Equation (38) was suggested a long time ago by Longuet-Higgins and Roberts 72 and seems like a major approximation at first sight. However, we have previously given theoretical arguments for the validity of Eq.…”

Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

“…where C is a constant of proportion. Equation (38) asserts that the off-diagonal Hamiltonian matrix element between the orthogonal site orbitals (φ k φ l ), H k l , is proportional to the orbital overlap of the corresponding non-orthogonal site orbitals (ϕ k , ϕ l ), S k l , where the two orbital pairs are related by the Lowdin transformation Eq. (8).…”

Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

“…However, we have previously given theoretical arguments for the validity of Eq. (38) in the small overlap regime using the exact expression for H k l within constrained density functional theory. 73 We have also previously assessed the accuracy of Eq.…”

Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

“…Friesner and co-workers noticed a good correlation between overlap and coupling for ET between bacteriochlorophyll cofactors, except for one cofactor pair where deviations were somewhat larger but still reasonable, 75 and Troisi used Eq. (38) for the estimation of electronic couplings between DNA base pairs. 76 Although Eq.…”

Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

“…The calculation of the latter is usually the time-limiting factor. A wide spectrum of electronic structure methods has been combined with SH ranging from ab initio wavefunction methods (multireference configuration interaction (MRCI), 32 CI, 33 complete active space self-consistent field (CASSCF) 32,34,35 ), to density functional theory (DFT)-based methods (time-dependent DFT (TDDFT), [36][37][38] open-shell Kohn Sham 39,40 ), to semiempirical approaches such as self-consistent charge density functional tight binding (SCC-DFTB) [41][42][43][44][45][46] and time-dependent SCC-DFTB, 47,48 OM3, 49,50 AM1, 51,52 and Pariser-Parr-Pople (PPP) electronic Hamiltonians. 5,53 Whereas the ab initio methods are in practice limited to very small systems, semi-empirical methods can be used to tackle large systems of several hundreds to thousands of atoms.…”

Section: Introductionmentioning

confidence: 99%

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FOB-SH: Fragment orbital-based surface hopping for charge carrier transport in organic and biological molecules and materials

Spencer

Gajdos

Blumberger

2016

The Journal of Chemical Physics

112

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We introduce a fragment orbital-based fewest switches surface hopping method, FOB-SH, designed to efficiently simulate charge carrier transport in strongly fluctuating condensed phase systems such as organic semiconductors and biomolecules. The charge carrier wavefunction is expanded and the electronic Hamiltonian constructed in a set of singly occupied molecular orbitals of the molecular sites that mediate the charge transfer. Diagonal elements of the electronic Hamiltonian (site energies) are obtained from a force field, whereas the off-diagonal or electronic coupling matrix elements are obtained using our recently developed analytic overlap method. We derive a general expression for the exact forces on the adiabatic ground and excited electronic state surfaces from the nuclear gradients of the charge localized electronic states. Applications to electron hole transfer in a model ethylene dimer and through a chain of ten model ethylenes validate our implementation and demonstrate its computational efficiency. On the larger system, we calculate the qualitative behaviour of charge mobility with change in temperature T for different regimes of the intermolecular electronic coupling. For small couplings, FOB-SH predicts a crossover from a thermally activated regime at low temperatures to a band-like transport regime at higher temperatures. For higher electronic couplings, the thermally activated regime disappears and the mobility decreases according to a power law. This is interpreted by a gradual loss in probability for resonance between the sites as the temperature increases. The polaron hopping model solved for the same system gives a qualitatively different result and underestimates the mobility decay at higher temperatures. Taken together, the FOB-SH methodology introduced here shows promise for a realistic investigation of charge carrier transport in complex organic, aqueous, and biological systems.

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Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

Section: B Off-diagonal Matrix Elements (Electronic Couplings) H Klmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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FOB-SH: Fragment orbital-based surface hopping for charge carrier transport in organic and biological molecules and materials

Spencer

Gajdos

Blumberger

2016

The Journal of Chemical Physics

112

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Intermolecular Photoinduced Electron Transfer in Biosystems: Impact of Conformational Transitions and Multiple Channels on Kinetics

Zanetti‐Polzi,

Pantazis,

Daidone

2024

ChemPhotoChem

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Estimating the kinetics of electron transfer (ET) processes in biologically relevant systems using theoretical‐computational methods remains a formidable task. This challenge arises from the inherent complexity of these systems, which makes it impractical to apply a fully quantum‐mechanical treatment. Hybrid quantum mechanical/classical mechanical computational approaches have been devised to enable the explicit simulation of electron transfer kinetics. This concept article focuses on a specific theoretical‐computational method employed in this context, namely the Perturbed Matrix Method (PMM), which has the merit of being able to include large‐scale conformational effects in the ET kinetics and potential multiple, alternative, ET channels. We describe its underlying physical principles, examine its advantages and limitations, and offer insights into its applications. Examples of the approach are discussed in the context of estimating photo‐induced electron transfer kinetics in proteins. The non‐exponential behavior observed in the presented case studies arises mainly from an active coupling with the environment fluctuations, but partly also stems from the presence of branching ET pathways.

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Spectroscopy and Photophysics Involving Transition Metal Complexes, Theoretical Perspectives

Daniel¹

2015

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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Nonadiabatic ab initio molecular dynamics using linear-response time-dependent density functional theory

Cited by 8 publications

References 43 publications

FOB-SH: Fragment orbital-based surface hopping for charge carrier transport in organic and biological molecules and materials

FOB-SH: Fragment orbital-based surface hopping for charge carrier transport in organic and biological molecules and materials

Intermolecular Photoinduced Electron Transfer in Biosystems: Impact of Conformational Transitions and Multiple Channels on Kinetics

Spectroscopy and Photophysics Involving Transition Metal Complexes, Theoretical Perspectives

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