Relaxation Of Excited Electronic States Research Articles

Excited State Decay Pathways of 2'-Deoxy-5-methylcytidine and Deoxycytidine Revisited in Solution: A Comprehensive Kinetic Study by Femtosecond Transient Absorption.

Methylated cytosine is proved to have an important role as an epigenetic signal in gene regulation and is often referred to "the fifth base of DNA". A comprehensive understanding of the electronic excited state relaxation in cytosine and its methylated derivatives is crucial for revealing UV-induced photodamage to the biological genome. Because of the existence of multiple closely lying "bright" and "dark" excited states, the decay pathways in these DNA nucleosides are the most complex and the least understood so far. In this study, femtosecond transient absorption with different excitation wavelengths (240-296 nm) was used to study the relaxation of excited electronic states of 5-methylcytosine (5mC) and 2'-deoxy-5-methylcytidine (5mdCyd) in phosphate buffered aqueous solution and in acetonitrile solution. Two distinct nonradiative decay channels were directly observed. The first one is a several picosecond internal conversion channel that involves two bright ππ* states (ππ*2 and ππ*1) when ππ*2 state is initially populated. The second channel contains the lower energy ππ*1 state and a so far experimental unidentified long-lived state which exhibits a several nanosecond lifetime. The long-lived state can only be accessed by the initially excited ππ*1 state. Inspired by this new discovery in 5mC and 5mdCyd, we revisited the decay of excited state of 2'-deoxycytidine (dCyd), revealing very similar decay pathways. Additionally, a well-known dark nOπ* state (carbonyl lone pair) with ∼30 ps lifetime is present in both decay channels in dCyd. With our detailed experimental results, we successfully reconcile the long history debate of cytosine excited state relaxation mechanism by pointing out that the reason for the complex dynamics under traditional 266 nm excitation is mixed signals from the above-mentioned two distinct decay pathways. Our findings lead to a dramatically different and new picture of electronic energy relaxation in 5mdCyd/dCyd and could help to understand photostability as well as UV-induced photodamage of these nucleotides and related DNAs.

Probing ultrafast dynamics in photoexcited pyrrole: timescales for 1πσ* mediated H-atom elimination

The heteroaromatic ultraviolet chromophore pyrrole is found as a subunit in a number of important biomolecules: it is present in heme, the non-protein component of hemoglobin, and in the amino acid tryptophan. To date there have been several experimental studies, in both the time- and frequency-domains, which have interrogated the excited state dynamics of pyrrole. In this work, we specifically aim to unravel any differences in the H-atom elimination dynamics from pyrrole across an excitation wavelength range of 250-200 nm, which encompasses: (i) direct excitation to the (formally electric dipole forbidden) 1(1)pisigma* (1A2) state; and (ii) initial photoexcitation to the higher energy 1 pipi* (1B2) state. This is achieved by using a combination of ultrafast time-resolved ion yield and time-resolved velocity map ion imaging techniques in the gas phase. Following direct excitation to 1(1)pisigma* (1A2) at 250 nm, we observe a single time-constant of 126 +/- 28 fs for N-H bond fission. We assign this to tunnelling out of the quasi-bound 3s Rydberg component of the 1(1)pisigma* (1A2) surface in the vertical Franck-Condon region, followed by non-adiabatic coupling through a 1(1)pisigma*/S(0) conical intersection to yield pyrrolyl radicals in their electronic ground state (C4H4N(X)) together with H-atoms. At 238 nm, direct excitation to, and N-H dissociation along, the 1(1)pisigma* (1A2) surface is observed to occur with a time-constant of 46 +/- 22 fs. Upon initial population of the 1pipi* (1B2) state at 200 nm, a rapid 1pipi* (1B2) --> 1(1)pisigma* (1A2) --> N-H fission process takes place within 52 +/- 12 fs. In addition to ultrafast N-H bond cleavage at 200 nm, we also observe the onset of statistical unimolecular H-atom elimination from vibrationally hot S(0) ground state species, formed after the relaxation of excited electronic states, with a time-constant of 1.0 +/- 0.4 ns. Analogous measurements on pyrrole-d1 reveal that these statistical H-atoms are released only through C-H bond cleavage.

Nonlinear dimensionality reduction for nonadiabatic dynamics: The influence of conical intersection topography on population transfer rates

Conical intersections play a critical role in the nonadiabatic relaxation of excited electronic states. However, there are an infinite number of these intersections and it is difficult to predict which are actually relevant. Furthermore, traditional descriptors such as intrinsic reaction coordinates and steepest descent paths often fail to adequately characterize excited state reactions due to their highly nonequilibrium nature. To address these deficiencies in the characterization of excited state mechanisms, we apply a nonlinear dimensionality reduction scheme (diffusion mapping) to generate reaction coordinates directly from ab initio multiple spawning dynamics calculations. As illustrated with various examples of photoisomerization dynamics, excited state reaction pathways can be derived directly from simulation data without any a priori specification of relevant coordinates. Furthermore, diffusion maps also reveal the influence of intersection topography on the efficiency of electronic population transfer, providing further evidence that peaked intersections promote nonadiabatic transitions more effectively than sloped intersections. Our results demonstrate the usefulness of nonlinear dimensionality reduction techniques as powerful tools for elucidating reaction mechanisms beyond the statistical description of processes on ground state potential energy surfaces.

Internal conversion to the electronic ground state occurs via two distinct pathways for pyrimidine bases in aqueous solution

The femtosecond transient absorption technique was used to study the relaxation of excited electronic states created by absorption of 267-nm light in all of the naturally occurring pyrimidine DNA and RNA bases in aqueous solution. The results reveal a surprising bifurcation of the initial excited-state population in <1 ps to two nonradiative decay channels within the manifold of singlet states. The first is the subpicosecond internal conversion channel first characterized in 2000. The second channel involves passage through a dark intermediate state assigned to a lowest-energy (1)npi* state. Approximately 10-50% of all photoexcited pyrimidine bases decay via the (1)npi* state, which has a lifetime of 10-150 ps. Three- to 6-fold-longer lifetimes are seen for pyrimidine nucleotides and nucleosides than for the corresponding free bases, revealing an unprecedented effect of ribosyl substitution on electronic energy relaxation. A small fraction of the (1)npi* population is proposed to undergo intersystem crossing to the lowest triplet state in competition with vibrational cooling, explaining the higher triplet yields observed for pyrimidine versus purine bases at room temperature. Some simple correlations exist between yields of the (1)npi* state and yields of some pyrimidine photoproducts, but more work is needed before the photochemical consequences of this state can be definitively determined. These findings lead to a dramatically different picture of electronic energy relaxation in single pyrimidine bases with important ramifications for understanding DNA photostability.

Study of relaxation times of polymethine dyes used for passive mode locking of solid-state lasers emitting between 750 and 850 nm

The relaxation times τ of the bleached states of polymethine dyes absorbing light in the 750 — 850-nm are determined by the direct pump — probe method. The effect of the dye structure and the solvent type on the relaxation time is discussed. The role of different intra- and intermolecular interactions in the relaxation of excited electronic states of the dyes is analysed. Polymethine dyes are found (with τ=11 — 75 ps) that are promising for passive mode locking in Cr3+:LiCaAlF6, Cr3+:KZnF3, and Cr3+:LiSrAlF6 crystal lasers.

Theoretical study of femtosecond pump–probe signals of nonstoichiometric alkali halide clusters

We present the outline of the ab-initio molecular dynamics method for adiabatic excited states which is suitable to treat the involved excited electronic states simultaneously with the motion of the nuclei. The method allows the simulation of time-resolved pump-probe signals and the analysis of the signals in terms of the underlying nuclear dynamics. Moreover, the timescales of the structural relaxation in excited electronic states vs. intramolecular vibrational relaxation processes can be estimated and the influence of the initial temperature of the cluster can be determined.

Electron–phonon interactions in CsCdBr3:Yb3+

Pronounced electron–phonon coupling is observed for the F7/22↔F5/22 4f transitions of Yb3+ doped into CsCdBr3. A comparison of the Raman spectrum and the luminescence excitation sideband accompanying the F7/22(0)→2F5/2(2′) crystal-field transition reveals vibrational properties of the [YbBr6] coordination unit that differ markedly from those of the CsCdBr3 host. In particular, the vibronic transition associated with the totally symmetric [YbBr6] stretching mode appears as a very weak feature at 191 cm−1 in the Raman spectrum, whereas the totally symmetric [CdBr6] stretching mode of the CsCdBr3 bulk, which appears as a strong feature at 162.5 cm−1 in the Raman spectrum, is only weakly discernible in the sideband. This is direct evidence for a large contribution from [YbBr6] local modes and a small contribution from bulk modes to the vibronic intensity. The intensity of the local mode is enhanced by approximately a factor of 2 in the Raman spectrum when the laser is tuned into resonance with the F7/22(0)→2F5/2(2′) absorption of Yb3+, providing direct confirmation of its assignment. The observation of the first and second members of a Franck–Condon progression for both the local and the bulk totally symmetric modes indicates that a Δ process, rather than an M process, induces the vibronic intensity. Huang–Rhys factors of Slocal=0.010±0.002 and Sbulk=0.15±0.03 were determined from the data, and reflect quite different electron–phonon coupling strengths. These results suggest that multiphonon relaxation of excited electronic states proceeds by the excitation of local modes of [YbBr6] followed by energy transfer to bulk modes of the lattice, possibly through a nonlinear coupling mechanism which is discussed briefly.

Intramolecular Vibrational Relaxation in Electronically Excited States

A density matrix approach for describing intramolecular dynamics, with special application to vibrational relaxation in excited electronic states, is presented. We derive the master equations governing intramolecular transfer of excitation energy between the states in a zeroth-order basis defined by considering the excitation and detection conditions in the time-resolved experiments. It is shown that, in this formalism, the memory function plays a central role. We note that the form of intramolecular memory is determined by the importance of quantum mechanical mixing of the zeroth-order states. A distinction is made between the subsystems of states with strong and weak mixing properties; while the former account for quasiperiodic character of coherent motion, the latter display a Markovian behavior. The physical conditions fixing the relative importance of quasiperiodic and statistical dynamics in individual systems are discussed. In the application to time resolved intramolecular vibrational relaxation, special consideration is given to the nature of the initially excited doorway states and the intermode couplings. The symmetry restrictions and the possible role of rotational motion in vibrational relaxation are also discussed, before considering the recent results obtained by Zewail et al. with anthracene in the first excited singlet state.

Multiphonon relaxation of rare-earth ions in beryllium-fluoride glass

Relaxation of excited electronic states of rare-earth ions by multiphonon emission was investigated in a beryllium-fluoride glass. Decay rates were measured from the transient fluorescence following pulsed laser excitation of selected states. The multiphonon emission rates exhibit an approximately exponential dependence on the energy gap to the next-lower state and are in general agreement with the phenomenological treatment of multiphonon processes.

Effects of vibrational relaxation on molecular electronic transitions

In this paper we explore the implications of the coupling between nonradiative electronic relaxation and vibrational relaxation in excited electronic states of large molecules. The physical model involved a two electronic level molecular system interacting with a harmonic medium via linear coupling terms in the molecular nuclear coordinates. Two models were advanced for the molecule-medium coupling which involve single phonon decay and alternatively double phonon (or rather phonon-vibron) decay. The functional form of our final results is independent of the specific model adopted for the vibrational relaxation. The molecular Hamiltonian and the intramolecular coupling were recast in terms of second quantization formalism where the nonadiabatic coupling operator was modified by a Franck Condon shift operator. The coupling between electronic and vibrational relaxation processes was formulated in terms of a generalized interaction picture, where the intramolecular coupling was treated to second order while the vibrational relaxation was handled to ``infinite order'' by the Wigner Weisskopf approximation as applied to the equations of motion for the nuclear operators for the normal molecular modes. The nonradiative decay rate of an excited electronic state was expressed in terms of a generalized time correlation function. We were able to demonstrate that our general expressions reduce to the (time independent) decay rate of a single vibronic level in the limit of slow vibrational relaxation and to a modified expression for the (time independent) decay rate of the thermally averaged electronic manifold in the limit of fast vibrational relaxation. In the general case of coupled electronic-vibrational relaxation the decay probability is time dependent. In the low temperature limit the nonradiative decay rate can be expressed in terms of a superposition of exponential functions.

Multiphonon decay of excited states of rare earth ions in crystals

Although the relaxation of excited electronic states through radiationless multiphonon processes has been well established by experiment, there are several serious problems concerning the current theoretical model in which the electron-phonon interaction is treated as a small perturbation, and the multiphonon transitions are attributed to high order expansion terms of perturbation theory. Here, we approach the problem in the framework of the adiabatic approximation. The rate of the multiphonon process is expressed in the form of the linear response time correlation function which is then evaluated by means of the saddle point approximation. The resulting expression predicts an approximately exponential dependence of the rate on the transition gap and a temperature dependence that agrees quantitatively with experiment.