Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation

Abstract

We report an efficient analytical implementation of first-order nonadiabatic derivative couplings between arbitrary Born–Oppenheimer states in the hybrid time-dependent density functional theory (TDDFT) framework using atom-centered basis functions.

Nonadiabatic dynamics with spin-flip vs linear-response time-dependent density functional theory: A case study for the protonated Schiff base C5H6NH2+

“…Whereas calculation of the derivative couplings is sometimes (incorrectly) perceived as being significantly more expensive than analytic gradients, in reality the calculation of h IJ for TDDFT adds only about 10% overhead on top of the cost of computing the gradients ∇R E I (R) and ∇R E J (R). 6,20…”

“…6(b) for this subset of trajectories, and then p(t) was fit to Eq. (20). Time constants and S 1 lifetimes are reported in Table III.…”

“…6 Despite its topology problems, however, conventional LR-TDDFT remains a widely-used approach in the context of trajectory surface hopping simulations of nonadiabatic molecular dynamics (NMD). [13][14][15][16][17][18][19][20] Provided that trajectories are halted before they can undergo internal conversion (IC) to the ground state, problems associated with incorrect topology may be avoided, but this con- straint is rather limiting insofar as the timescale for IC is one of the most basic questions that one might wish to answer using NMD simulations. As a counterpoint, there might be reason for optimism given that most nonadiabatic events likely occur near conical seams, where the energy gap is small, as opposed to occurring at a conical seam, where the energy gap is zero but which occupies a vanishingly small volume in the configuration space of a polyatomic molecule.…”

Excitation energy transport in DNA modelled by multi-chromophoric field-induced surface hopping

“…For the heteropolymorphic (dAdT) 18 : (dAdT) 18 duplexes Kohler et al determined a lifetime of 51 ps, which is 3 times shorter than for the homopolymeric duplexes 12 , and femtosecond fluorescence spectroscopy reveals a wavelength dependent increase of the of the excited state lifetime from 0.5 ps at 330 nm to 3.3 ps at 420 nm 11 . Thus the overall excited state lifetime is found to be much longer than for the isolated nucleobases, which exhibit radiationless decay times of a few 100 fs to 1 ps [91][92][93][94][95][96] . Interestingly, the fast decaying component of the excited state population with a time constant of 0.7 ps is close to the lifetime of 0.46 ps found for equimolar mixtures of deoxyadenosine monophosphate (dAMP) and thymidine monophosphate (TMP), and the fast decaying component (0.13 ps) of the S L population is the same as for pure dAMP solutions 97 .…”

Nonadiabatic dynamics with spin-flip versus linear-response time-dependent density functional theory: A case study for the protonated Schiff base C5H6NH2+

“…Time constants τ d and τ e and total lifetime of the S1 state of PSB3 (all in fs), obtained by fitting the population data in Fig.6using Eq (20)…”