260 research outputs found
Coherent and incoherent dynamics in excitonic energy transfer: correlated fluctuations and off-resonance effects
We study the nature of the energy transfer process within a pair of coupled
two-level systems (donor and acceptor) subject to interactions with the
surrounding environment. Going beyond a standard weak-coupling approach, we
derive a master equation within the polaron representation that allows for
investigation of both weak and strong system-bath couplings, as well as
reliable interpolation between these two limits. With this theory, we are then
able to explore both coherent and incoherent regimes of energy transfer within
the donor-acceptor pair. We elucidate how the degree of correlation in the
donor and acceptor fluctuations, the donor-acceptor energy mismatch, and the
range of the environment frequency distribution impact upon the energy transfer
dynamics. In the resonant case (no energy mismatch) we describe in detail how a
crossover from coherent to incoherent transfer dynamics occurs with increasing
temperature [A. Nazir, Phys. Rev. Lett. 103, 146404 (2009)], and we also
explore how fluctuation correlations are able to protect coherence in the
energy transfer process. We show that a strict crossover criterion is harder to
define when off-resonance, though we find qualitatively similar population
dynamics to the resonant case with increasing temperature, while the amplitude
of coherent population oscillations also becomes suppressed with growing site
energy mismatch.Comment: 14 pages, 7 figures, builds upon PRL 103, 146404 (2009)
(arXiv:0906.0592). Comments welcome. V2 - Section IV shortened to improve
presentation, references updated, new Imperial College affiliation added for
A. Nazir. Published versio
Accurate prediction of gene feedback circuit behavior from component properties
A basic assumption underlying synthetic biology is that analysis of genetic circuit elements, such as regulatory proteins and promoters, can be used to understand and predict the behavior of circuits containing those elements. To test this assumption, we used time‐lapse fluorescence microscopy to quantitatively analyze two autoregulatory negative feedback circuits. By measuring the gene regulation functions of the corresponding repressor–promoter interactions, we accurately predicted the expression level of the autoregulatory feedback loops, in molecular units. This demonstration that quantitative characterization of regulatory elements can predict the behavior of genetic circuits supports a fundamental requirement of synthetic biology
Finite-temperature time-dependent variation with multiple Davydov states
The Dirac-Frenkel time-dependent variational approach with Davydov Ans\"atze
is a sophisticated, yet efficient technique to obtain an acuurate solution to
many-body Schr\"odinger equations for energy and charge transfer dy- namics in
molecular aggregates and light-harvesting complexes. We extend this variational
approach to finite temperatures dynamics of the spin-boson model by adopting a
Monte Carlo importance sampling method. In or- der to demonstrate the
applicability of this approach, we compare real-time quantum dynamics of the
spin-boson model calculated with that from numerically exact iterative
quasiadiabatic propagator path integral (QUAPI) technique. The comparison shows
that our variational approach with the single Davydov Ans\"atze is in excellent
agreement with the QUAPI method at high temperatures, while the two differ at
low temperatures. Accuracy in dynamics calculations employing a multitude of
Davydov trial states is found to improve substantially over the single Davydov
Ansatz, especially at low temperatures. At a moderate computational cost, our
variational approach with the multiple Davydov Ansatz is shown to provide
accurate spin-boson dynamics over a wide range of temperatures and bath
spectral densities.Comment: 8 pages, 3 figure
Multiple-charge transfer and trapping in DNA dimers
We investigate the charge transfer characteristics of one and two excess
charges in a DNA base-pair dimer using a model Hamiltonian approach. The
electron part comprises diagonal and off-diagonal Coulomb matrix elements such
a correlated hopping and the bond-bond interaction, which were recently
calculated by Starikov [E. B. Starikov, Phil. Mag. Lett. {\bf 83}, 699 (2003)]
for different DNA dimers. The electronic degrees of freedom are coupled to an
ohmic or a super-ohmic bath serving as dissipative environment. We employ the
numerical renormalization group method in the nuclear tunneling regime and
compare the results to Marcus theory for the thermal activation regime. For
realistic parameters, the rate that at least one charge is transferred from the
donor to the acceptor in the subspace of two excess electrons significantly
exceeds the rate in the single charge sector. Moreover, the dynamics is
strongly influenced by the Coulomb matrix elements. We find sequential and pair
transfer as well as a regime where both charges remain self-trapped. The
transfer rate reaches its maximum when the difference of the on-site and
inter-site Coulomb matrix element is equal to the reorganization energy which
is the case in a GC-GC dimer. Charge transfer is completely suppressed for two
excess electrons in AT-AT in an ohmic bath and replaced by damped coherent
electron-pair oscillations in a super-ohmic bath. A finite bond-bond
interaction alters the transfer rate: it increases as function of when
the effective Coulomb repulsion exceeds the reorganization energy (inverted
regime) and decreases for smaller Coulomb repulsion
Effects of tunnelling and asymmetry for system-bath models of electron transfer
We apply the newly derived nonadiabatic golden-rule instanton theory to
asymmetric models describing electron-transfer in solution. The models go
beyond the usual spin-boson description and have anharmonic free-energy
surfaces with different values for the reactant and product reorganization
energies. The instanton method gives an excellent description of the behaviour
of the rate constant with respect to asymmetry for the whole range studied. We
derive a general formula for an asymmetric version of Marcus theory based on
the classical limit of the instanton and find that this gives significant
corrections to the standard Marcus theory. A scheme is given to compute this
rate based only on equilibrium simulations. We also compare the rate constants
obtained by the instanton method with its classical limit to study the effect
of tunnelling and other quantum nuclear effects. These quantum effects can
increase the rate constant by orders of magnitude.Comment: 10 pages, 3 figure
Generalization of escape rate from a metastable state driven by external cross-correlated noise processes
We propose generalization of escape rate from a metastable state for
externally driven correlated noise processes in one dimension. In addition to
the internal non-Markovian thermal fluctuations, the external correlated noise
processes we consider are Gaussian, stationary in nature and are of
Ornstein-Uhlenbeck type. Based on a Fokker-Planck description of the effective
noise processes with finite memory we derive the generalized escape rate from a
metastable state in the moderate to large damping limit and investigate the
effect of degree of correlation on the resulting rate. Comparison of the
theoretical expression with numerical simulation gives a satisfactory agreement
and shows that by increasing the degree of external noise correlation one can
enhance the escape rate through the dressed effective noise strength.Comment: 9 pages, 1 figur
Transport and optical response of molecular junctions driven by surface plasmon-polaritons
We consider a biased molecular junction subjected to external time-dependent
electromagnetic field. The field for two typical junction geometries (bowtie
antennas and metal nanospheres) is calculated within finite-difference
time-domain technique. Time-dependent transport and optical response of the
junctions is calculated within non-equilibrium Green's function approach
expressed in a form convenient for description of multi-level systems. We
present numerical results for a two-level (HOMO-LUMO) model, and discuss
influence of localized surface plasmon polariton modes on transport.Comment: 9 pages, 6 figure
Quantum Transition State Theory for proton transfer reactions in enzymes
We consider the role of quantum effects in the transfer of hyrogen-like
species in enzyme-catalysed reactions. This study is stimulated by claims that
the observed magnitude and temperature dependence of kinetic isotope effects
imply that quantum tunneling below the energy barrier associated with the
transition state significantly enhances the reaction rate in many enzymes. We
use a path integral approach which provides a general framework to understand
tunneling in a quantum system which interacts with an environment at non-zero
temperature. Here the quantum system is the active site of the enzyme and the
environment is the surrounding protein and water. Tunneling well below the
barrier only occurs for temperatures less than a temperature which is
determined by the curvature of potential energy surface near the top of the
barrier. We argue that for most enzymes this temperature is less than room
temperature. For physically reasonable parameters quantum transition state
theory gives a quantitative description of the temperature dependence and
magnitude of kinetic isotope effects for two classes of enzymes which have been
claimed to exhibit signatures of quantum tunneling. The only quantum effects
are those associated with the transition state, both reflection at the barrier
top and tunneling just below the barrier. We establish that the friction due to
the environment is weak and only slightly modifies the reaction rate.
Furthermore, at room temperature and for typical energy barriers environmental
degrees of freedom with frequencies much less than 1000 cm do not have a
significant effect on quantum corrections to the reaction rate.Comment: Aspects of the article are discussed at
condensedconcepts.blogspot.co
Assigning the right credit to the wrong action: compulsivity in the general population is associated with augmented outcome-irrelevant value-based learning.
Funder: NIHR Senior InvestigatorCompulsive behavior is enacted under a belief that a specific act controls the likelihood of an undesired future event. Compulsive behaviors are widespread in the general population despite having no causal relationship with events they aspire to influence. In the current study, we tested whether there is an increased tendency to assign value to aspects of a task that do not predict an outcome (i.e., outcome-irrelevant learning) among individuals with compulsive tendencies. We studied 514 healthy individuals who completed self-report compulsivity, anxiety, depression, and schizotypal measurements, and a well-established reinforcement-learning task (i.e., the two-step task). As expected, we found a positive relationship between compulsivity and outcome-irrelevant learning. Specifically, individuals who reported having stronger compulsive tendencies (e.g., washing, checking, grooming) also tended to assign value to response keys and stimuli locations that did not predict an outcome. Controlling for overall goal-directed abilities and the co-occurrence of anxious, depressive, or schizotypal tendencies did not impact these associations. These findings indicate that outcome-irrelevant learning processes may contribute to the expression of compulsivity in a general population setting. We highlight the need for future research on the formation of non-veridical action-outcome associations as a factor related to the occurrence and maintenance of compulsive behavior
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Credit assignment to state-independent task representations and its relationship with model-based decision making.
Model-free learning enables an agent to make better decisions based on prior experience while representing only minimal knowledge about an environment's structure. It is generally assumed that model-free state representations are based on outcome-relevant features of the environment. Here, we challenge this assumption by providing evidence that a putative model-free system assigns credit to task representations that are irrelevant to an outcome. We examined data from 769 individuals performing a well-described 2-step reward decision task where stimulus identity but not spatial-motor aspects of the task predicted reward. We show that participants assigned value to spatial-motor representations despite it being outcome irrelevant. Strikingly, spatial-motor value associations affected behavior across all outcome-relevant features and stages of the task, consistent with credit assignment to low-level state-independent task representations. Individual difference analyses suggested that the impact of spatial-motor value formation was attenuated for individuals who showed greater deployment of goal-directed (model-based) strategies. Our findings highlight a need for a reconsideration of how model-free representations are formed and regulated according to the structure of the environment
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