Long-lived oscillatory incoherent electron dynamics in molecules: trans-polyacetylene oligomers

We identify an intriguing feature of the electron-vibrational dynamics of molecular systems via a computational examination of trans-polyacetylene oligomers. Here, via the vibronic interactions, the decay of an electron in the conduction band resonantly excites an electron in the valence band, and vice versa, leading to oscillatory exchange of electronic population between two distinct electronic states that lives for up to tens of picoseconds. The oscillatory structure is reminiscent of beating patterns between quantum states and is strongly suggestive of the presence of long-lived molecular electronic coherence. Significantly, however, a detailed analysis of the electronic coherence properties shows that the oscillatory structure arises from a purely incoherent process. These results were obtained by propagating the coupled dynamics of electronic and vibrational degrees of freedom in a mixed quantum-classical study of the Su-Schrieffer-Heeger Hamiltonian for polyacetylene. The incoherent process is shown to occur between degenerate electronic states with distinct electronic configurations that are indirectly coupled via a third auxiliary state by vibronic interactions. A discussion of how to construct electronic superposition states in molecules that are truly robust to decoherence is also presented

Variable-angle electron spectroscopic studies of various polyatomic molecular systems

The complementary techniques of low-energy, variable-angle electron-impact spectroscopy and ultraviolet variable-angle photoelectron spectroscopy have been used to study the electronic spectroscopy and structure of several series of molecules. Electron-impact studies were performed at incident beam energies between 25 eV and 100 eV and at scattering angles ranging from 0° to 90°. The energy-loss regions from 0 eV to greater than 15 eV were studied. Photoelectron spectroscopic studies were conducted using a HeI radiation source and spectra were measured at scattering angles from 45° to 90°. The molecules studied were chosen because of their spectroscopic, chemical, and structural interest. The operation of a new electron-impact spectrometer with multiple-mode target source capability is described. This spectrometer has been used to investigate the spin-forbidden transitions in a number of molecular systems.

The electron-impact spectroscopy of the six chloro-substituted ethylenes has been studied over the energy-loss region from 0-15 eV. Spin-forbidden excitations corresponding to the π → π*, N → T transition have been observed at excitation energies ranging from 4.13 eV in vinyl chloride to 3.54 eV in tetrachloroethylene. Symmetry-forbidden transitions of the type π → np have been oberved in trans-dichloroethyene and tetrachlor oethylene. In addition, transitions to many states lying above the first ionization potential were observed for the first time. Many of these bands have been assigned to Rydberg series converging to higher ionization potentials. The trends observed in the measured transition energies for the π → π*, N → T, and N → V as well as the π → 3s excitation are discussed and compared to those observed in the methyl- and fluoro- substituted ethylenes.

The electron energy-loss spectra of the group VIb transition metal hexacarbonyls have been studied in the 0 eV to 15 eV region. The differential cross sections were obtained for several features in the 3-7 eV energy-loss region. The symmetry-forbidden nature of the ¹A_1g → ¹A_1g, 2t_2g(π) → 3t_2g(π*) transition in these compounds was confirmed by the high-energy, low-angle behavior of their relative intensities. Several low lying transitions have been assigned to ligand field transitions on the basis of the energy and angular behavior of the differential cross sections for these transitions. No transitions which could clearly be assigned to singlet → triplet excitations involving metal orbitals were located. A number of states lying above the first ionization potential have been observed for the first time. A number of features in the 6-14 eV energy-loss region of the spectra of these compounds correspond quite well to those observed in free CO.

A number of exploratory studies have been performed. The π → π*, N → T, singlet → triplet excitation has been located in vinyl bromide at 4.05 eV. We have also observed this transition at approximately 3.8 eV in a cis-/trans- mixture of the 1,2-dibromoethylenes. The low-angle spectrum of iron pentacarbonyl was measured over the energy-loss region extending from 2-12 eV. A number of transitions of 8 eV or greater excitation energy were observed for the first time. Cyclopropane was also studied at both high and low angles but no clear evidence for any spin- forbidden transitions was found. The electron-impact spectrum of the methyl radical resulting from the pyrolysis of tetramethyl tin was obtained at 100 eV incident energy and at 0° scattering angle. Transitions observed at 5.70 eV and 8.30 eV agree well with the previous optical results. In addition, a number of bands were observed in the 8-14 eV region which are most likely due to Rydberg transitions converging to the higher ionization potentials of this molecule. This is the first reported electron-impact spectrum of a polyatomic free radical.

Variable-angle photoelectron spectroscopic studies were performed on a series of three-membered-ring heterocyclic compounds. These compounds are of great interest due to their highly unusual structure. Photoelectron angular distributions using HeI radiation have been measured for the first time for ethylene oxide and ethyleneimine. The measured anisotropy parameters, β, along with those measured for cyclopropane were used to confirm the orbital correlations and photoelectron band assignments. No high values of β similar to those expected for alkene π orbitals were observed for the Walsh or Forster-Coulson-Moffit type orbitals.

A study of T = 2 states in ^(12)B, ^(12)C, ^(20)F and ^(28)Al

The lowest T = 2 states have been identified and studied in the nuclei ¹²C, ¹²B, ²⁰F and and ²⁸Al. The first two of these were produced in the reactions ¹⁴C(p,t)¹²C and ¹⁴C (p,³He)¹²B, at 50.5 and 63.4 MeV incident proton energy respectively, at the Oak Ridge National Laboratory. The T = 2 states in ²⁰F and ²⁸Al were observed in (³He,p) reactions at 12-MeV incident energy, with the Caltech Tandem accelerator.

The results for the four nuclei studied are summarized below:

(1) ¹²C: the lowest T = 2 state was located at an excitation energy of 27595 ± 20 keV, and has a width less than 35 keV.

(2) ¹²B: the lowest T = 2 state was found at an excitation energy of 12710 ± 20 keV. The width was determined to be less than 54 keV and the spin and parity were confirmed to be 0⁺. A second ¹²B state (or doublet) was observed at an excitation energy of 14860 ± 30 keV with a width (if the group corresponds to a single state) of 226 ± 30 keV.

(3) ²⁰F: the lowest T = 2 state was observed at an excitation of 6513 ± 5 keV; the spin and parity were confirmed to be 0⁺. A second state, tentatively identified as T = 2 from the level spacing, was located at 8210 ± 6 keV.

(4) ²⁸Al: the lowest T = 2 state was identified at an excitation of 5997 ± 6 keV; the spin and parity were confirmed to be 0⁺. A second state at an excitation energy of 7491 ± 11 keV is tentatively identified as T = 2, with a corresponding (tentative) spin and parity assignment J^π = 2⁺.

The results of the present work and the other known masses of T = 2 states and nuclei for 8 ≤ A ≤ 28 are summarized, and massequation coefficients have been extracted for these multiplets. These coefficients were compared with those from T = 1 multiplets, and then used to predict the mass and stability of each of the unobserved members of the T = 2 multiplets.

A study of T=1, T=3/2, and T=2 states in some light nuclei using (He^3,n) reactions

The (He³, n) reactions on B¹¹, N¹⁵, O¹⁶, and O¹⁸ targets have been studied using a pulsed-beam time-of-flight spectrometer. Special emphasis was placed upon the determination of the excitation energies and properties of states with T = 1 (in Ne¹⁸), T = 3/2 (in N¹³ and F¹⁷) and T = 2 (in Ne²⁰). The identification of the T = 3/2 and T = 2 levels is based on the structure of these states as revealed by intensities and shapes of angular distributions. The reactions are interpreted in terms of double stripping theory. Angular distributions have been compared with plane and distorted wave stripping theories. Results for the four reactions are summarized below:

1) O¹⁶ (He³, n). The reaction has been studied at incident energies up to 13.5 MeV and two previously unreported levels in Ne¹⁸ were observed at E_x = 4.55 ± .015 MeV (Γ = 70 ± 30 keV) and E_x = 5.14 ± .018 MeV (Γ = 100 ± 40 keV).

2) B¹¹ (He³, n). The reaction has been studied at incident energies up to 13.5 MeV. Three T = 3/2 levels in N¹³ have been identified at E_x = 15.068 ± .008 MeV (Γ ˂ 15 keV), E_x = 18.44 ± .04, and E_x 18.98 ± .02 MeV (Γ = 40 ± 20 keV).

3) N¹⁵ (He³, n). The reaction has been studied at incident energies up to 11.88 MeV. T = 3/2 levels in F¹⁷ have been identified at E_x = 11.195 ± .007 MeV (Γ ˂ 20 keV), E_x = 12.540 ± .010 MeV (Γ ˂ 25 keV), and E_x = 13.095 ± .009 MeV (Γ ˂ 25 keV).

4) O¹⁸ (He³, n). The reaction has been studied at incident energies up to 9.0 MeV. The excitation energy of the lowest T = 2 level in Ne²⁰ has been found to be 16.730 ± .006 MeV (Γ ˂ 20 keV).

Angular distributions of the transitions leading to the above higher isospin states are well described by double stripping theory. Analog correspondences are established by comparing the present results with recent studies (t, p) and (He³, p) reactions on the same targets.

Nd3+螯合物的含氢有机溶液光谱性能研究

Tris-thenoyltrifluroacetonate of Nd3+ has been prepared and dissolved in DMF solation with very high concentration, and the contained hydrogen has not been substituted by deuterium. The absorption spectrum, emission spectrum, and fluorescence lifetime of the solution were measured. Very obvious characteristic fluorescence peaks were observed at 898 and 1058 nm. Based on Judd-Ofelt theory, three intensity parameters were obtained: Omega(2) = 4.9 x 10(-20) cm(2), Omega(4) = 5.1 x 10(-20) cm(2) and Omega(6) = 2.5 x 10(-20) cm(2). Line strengths S-cal, oscillator strengths f(cal), radiative transition probabilities A(ed), radiative lifetimes tau(r) and branch ratios beta were calculated too. The measured lifetime tau of 1058 nm peak is 460 mu s, and that of 898 nm 505 mu s. Comparison between theoretically computed radiative lifetime tau(r)(682 mu s) and the measured lifetime indicates that the non-radiative transition probability of the solution is very low and the fluorescence quantum efficiency very high. High values of three intensity parameters prove the high asymmetric surroundings of Nd3+, which is important for Nd3+ to absorb the excitation energy. Spectropic quality factor Omega(4)/Omega(6) > 1 makes radiation at 898 nm stronger than at 1058 nm.

Photosynthetic responses of trees in high-elevation forests: comparing evergreen species along an elevation gradient in the Central Andes

Plant growth at extremely high elevations is constrained by high daily thermal amplitude, strong solar radiation and water scarcity. These conditions are particularly harsh in the tropics, where the highest elevation treelines occur. In this environment, the maintenance of a positive carbon balance involves protecting the photosynthetic apparatus and taking advantage of any climatically favourable periods. To characterize photoprotective mechanisms at such high elevations, and particularly to address the question of whether these mechanisms are the same as those previously described in woody plants along extratropical treelines, we have studied photosynthetic responses in Polylepis tarapacana Philippi in the central Andes (18 degrees S) along an elevational gradient from 4300 to 4900 m. For comparative purposes, this gradient has been complemented with a lower elevation site (3700 m) where another Polylepis species (P. rugulosa Bitter) occurs. During the daily cycle, two periods of photosynthetic activity were observed: one during the morning when, despite low temperatures, assimilation was high; and the second starting at noon when the stomata closed because of a rise in the vapour pressure deficit and thermal dissipation is prevalent over photosynthesis. From dawn to noon there was a decrease in the content of antenna pigments (chlorophyll b and neoxanthin), together with an increase in the content of xanthophyll cycle carotenoids. These results could be caused by a reduction in the antenna size along with an increase in photoprotection. Additionally, photoprotection was enhanced by a partial overnight retention of de-epoxized xanthophylls. The unique combination of all of these mechanisms made possible the efficient use of the favourable conditions during the morning while still providing enough protection for the rest of the day. This strategy differs completely from that of extratropical mountain trees, which uncouple light-harvesting and energy-use during long periods of unfavourable, winter conditions.

Status of vibrational structure in Ni62

Measurements consisting of γ-ray excitation functions and angular distributions were performed using the (n,n′γ) reaction on Ni62. The excitation function data allowed us to check the consistency of the placement of transitions in the level scheme. From γ-ray angular distributions, the lifetimes of levels up to ~3.8 MeV in excitation energy were extracted with the Doppler-shift attenuation method. The experimentally deduced values of reduced transition probabilities were compared with the predictions of the quadrupole vibrator model and with large-scale shell model calculations in the fp shell configuration space. Two-phonon states were found to exist with some notable deviation from the predictions of the quadrupole vibrator model, but no evidence for the existence of three-phonon states could be established. Z=28 proton core excitations played a major role in understanding the observed structure. © 2011 American Physical Society.

Raman scattering efficiency of graphene

We determine the Raman scattering efficiency of the G and 2D peaks in graphene. Three substrates are used: silicon covered with 300 or 90 nm oxide, and calcium fluoride (CaF2). On Si/SiOx, the areas of the G and 2D peak show a strong dependence on the substrate due to interference effects, while on CaF2 no significant dependence is detected. Unintentional doping is reduced by placing graphene on CaF2. We determine the Raman scattering efficiency by comparison with the 322 cm -1 peak area of CaF2. At 2.41 eV, the Raman efficiency of the G peak is ∼200×10-5 m-1Sr-1, and changes with the excitation energy to the power of 4. The 2D Raman efficiency is at least one order of magnitude higher than that of the G peak, with a different excitation energy dependence. © 2013 American Physical Society.

Polarization dependence of double resonant Raman scattering band in bilayer graphene

The polarization dependence of the double resonant Raman scattering (2D) band in bilayer graphene (BLG) is studied as a function of the excitation laser energy. It has been known that the complex shape of the 2D band of BLG can be decomposed into four Lorentzian peaks with different Raman frequency shifts attributable to four individual scattering paths in the energy-momentum space. From our polarization dependence study, however, we reveal that each of the four different peaks is actually doubly degenerate in its scattering channels, i.e., two different scattering paths with similar Raman frequency shifts for each peak. We find theoretically that one of these two paths, ignored for a long time, has a small contribution to their scattering intensities but are critical in understanding their polarization dependences. Because of this, the maximum-to-minimum intensity ratios of the four peaks show a strong dependence on the excitation energy, unlike the case of single-layer graphene (SLG). Our findings thus reveal another interesting aspect of electron-phonon interactions in graphitic systems. © 2014 Elsevier Ltd. All rights reserved.

Carrier spin relaxation in (Ga, Mn) As at room temperature

In this paper, the excitation energy density dependence of carrier spin relaxation is studied at room temperature for the as-grown and annealed (Ga, Mn) As samples using femtosecond time-resolved pump-probe Kerr spectroscopy. It is found that spin relaxation lifetime of electrons lengthens with increasing excitation energy density for both samples, and the annealed ( Ga, Mn) As has shorter carrier recombination and electron spin relaxation lifetimes as well as larger Kerr rotation angle than the as-grown ( Ga. Mn) As under the same excitation condition. which shows that DP mechanism is dominant in the spin relaxation process for ( Ga, Mn)As at room temperature. The enhanced ultrafast Kerr effect in the annealed (Ga,Mn)As shows the potential application of the annealed ( Ga, Mn) As in ultrafast all-optical spin switches, and also provides a further evidence for the p-d exchange mechanism of the ferromagnetic origin of (Ga, Mn) As.

Unusual carrier thermalization in a dilute GaAs1-xNx alloy

Photoluminescence (PL) properties of the E-0, E-0+Delta(0), and E+ bands in an x=0.62% GaAs1-xNx alloy were investigated in detail, including their peak position, linewidth, and line shape dependences on the excitation energy, excitation power, and temperature, using micro-PL. The hot electrons within the E+ band are found to exhibit highly unusual thermalization, which results in a large blueshift in its PL peak energy by >2k(B)T, suggesting peculiar density of states and carrier dynamics of the E+ band.

Anti-Stokes photoluminescence in ZnO microcrystal

Low temperature (10 K) strong anti-Stokes photoluminescence (ASPL) of ZnO microcrystal excited by low power cw 532 nm laser is reported here. Energy upconversion of 1.1 eV is obtained in our experiment with no conventional nonlinear effect. Through the study of the normal photoluminescence and temperature dependence of ASPL we conclude that the green band luminescence in ZnO is related to deep donor to valance band transition. Using the two-step two-photon absorption model, we provide a plausible mechanism leading to the ASPL phenomenon in our experiment. (c) 2006 American Institute of Physics.

Selectively excited photoluminescence of GaAs1-xNx single quantum wells

GaAsN bulk and GaAsN/GaAs single quantum wells grown by molecular beam epitaxy are studied by selectively excited photoluminescence (PL) measurements. A significant difference is observed in the PL spectra when the excitation energy is set below or above the band gap of GaAs for the GaAsN/GaAs quantum well samples, while the spectral features of GaAsN bulk are not sensitive to the excitation energy. The observed difference in PL of the GaAsN/GaAs quantum well samples is attributed to the exciton localization effect at the GaAsN/GaAs interfaces, which is directly correlated with the transfer and trap processes of the photogenerated carriers from GaAs into GaAsN through the heterointerfaces. This interface-related exciton localization effect can be greatly reduced by a rapid thermal annealing process, making the PL be dominated by the intrinsic delocalized transition in GaAsN/GaAs. (C) 2003 American Institute of Physics.

Study of optical properties in GaAs1-xSbx/GaAs single quantum wells

GaAsSb/GaAs single quantum wells (SQWs) grown by molecular beam epitaxy are studied by selectively-excited photoluminescence (SEPL) measurement. For the first time, we have simultaneously observed the PL, from both type I and type II transitions in GaAsSb/GaAs heterostructure in the SEPL. The two transitions exhibit different PL, behaviours under different excitation energy. As expected, the peak energy of type I emission remains constant in the whole excitation energy range we used, while type U transition shows a significant blue shift with increasing excitation energy. The observed blue shift is well explained in terms of electron-hole charge separation model at the interface. Time-resolved(TR) PL exhibits more type 11 characteristic of GaAsSb/GaAs QW. Moreover, the results of the excitation-power-dependent PL and TRPL provide more direct information on the type-II nature of the band alignment in GaAsSb/GaAs quantum-well structures. By combining the experimental results with some simple calculations, we have obtained the strained and unstrained valence band offsets of Q(v) = 1.145 and Q(v)(0) = 0. 76 in our samples, respectively.

Selectively excited photoluminescence of GaAs1-xSbx/GaAs single quantum wells

GaAsSb/GaAs single quantum wells grown by molecular-beam epitaxy are studied by selectively excited photoluminescence measurements. We have simultaneously observed the photoluminescence (PL) from both type-I and type-II transitions in the samples. The two transitions exhibit different PL behavior under different excitation energies. As expected, the peak energy of the type-I emission remains constant in the entire excitation energy range we used, while the type-II transition shows a significant blueshift with increasing excitation energy. The observed blueshift can be well explained by an electron-hole charge separation model at interface. This result, along with the excitation-power-dependent PL and the measured longer carrier decay time, provides more direct information on the type-II nature of the band alignment in GaAsSb/GaAs quantum well structures. (C) 2002 American Institute of Physics.