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The model Hamiltonian approach of Köppel et al. [Adv. Chem. Phys. 57, 59 (1984)] is used to analyze the electronic spectroscopy of the nitrate radical (NO3). Simulations of negative ion photodetachment of NO3-, the X 2A2′←B 2E′ dispersed fluorescence spectrum of NO3, and the B 2E′←X 2A2′ absorption spectrum are all in qualitative agreement with experiment, indicating that the model Hamiltonian contains most or all of the essential physics that govern the strongly coupled X 2A2′ and B 2E′ electronic states of the radical. All 14 bands seen in the dispersed fluorescence spectrum below 2600 cm-1 are assigned based on the simulations, filling in a few gaps left by previous work, and 7 additional bands below 4000 cm-1 are tentatively assigned. The assignment is predicated on the assumption that the ν3 level of NO3 is near 1000 cm-1 rather than 1492 cm-1 as is presently believed. Support for this reassignment (which associates the 1492 cm-1 band with the ν1+ν4 level) comes from both the model Hamiltonian spectrum and a Fourier-transform infrared feature at 2585 cm-1 that is consistent with the large and positive cross anharmonicity between ν1 and ν4 needed for the alternative 1492 cm-1 assignment. An apparent systematic deficiency exists in the treatment of the model Hamiltonian for levels involving ν4. A discussion of the correlation between energy levels in the rigid D3h and C2v limits is illustrative, and provides insight into just how hard it is to treat the degenerate bending coordinate (q4) of NO3 accurately. [ABSTRACT FROM AUTHOR]

The entire ultraviolet-visible absorption spectrum of benzophenone in water is studied and compared with the same spectrum in gas phase. Five transitions are considered, and the corresponding solvatochromic shifts are obtained and compared to experiment. Using a sequential procedure of Monte Carlo simulations and quantum mechanical calculations, liquid configurations were generated and an averaged spectrum of the solution was calculated. The solute polarization was included by an iterative procedure where the atomic charges of the solute were obtained as an average with the solvent distribution. The calculated average dipole moment of benzophenone in water, with MP2/6-31++G(d,p), converges to the value of 5.84±0.05 D, 88% larger than the gas-phase value of 3.11 D. Using 100 statistically uncorrelated configurations and solvation shells with 235 explicit water molecules selected by a minimum-distance distribution of solvent shells, instead of the usual radial distribution, the excitation energies were obtained from solute-solvent all-valence-electron INDO/CIS calculations. The shift of the weak n-π* transition is obtained as 2045±40 cm-1 and the strong and broad π-π* shift as -1790±30 cm-1. These results are in good agreement with the experimental values of 2200 and -1600 cm-1, respectively. Standard procedure used by common force fields to generate atomic charges to describe the electrostatic moments of the solute, with HF/6-31G(d), gives a dipole moment of 3.64 D. Using these standard charges in the simulation, the average shifts are calculated as 1395±35 and -1220±25 cm-1, both about 600 cm-1 smaller in magnitude than those obtained with the average converged fully polarized solute. The influence of the solute polarization in the solute-solvent interaction and, in particular, in solute-solvent hydrogen bonds is analyzed. [ABSTRACT FROM AUTHOR]

Mixed quantum-classical statistical mechanics is employed to calculate dipole moment correlation function and linear absorption spectra. A quantum two-level subsystem interacting with quantum vibrations (primary oscillators) which in turn are coupled to a classical bath composed of infinite set of harmonic oscillators is used as a dissipative system. Starting with mixed quantum-classical Liouville equation for the evaluation of the mixed quantum-classical dipole moment correlation function and using coherent states and the inverse of Baker-Campbell-Hausdorf formula to evaluate the trace over the primary oscillators, whereby, a closed analytical expression for the electronic dipole moment correlation function is obtained. Illustrations of several absorption spectra at different temperatures are provided. An approximate optical four-point correlation is obtained in the high temperature limit. A strategy for deriving an exact optical four-point correlation is suggested. [ABSTRACT FROM AUTHOR]

The UV/visible spectra of a series of indigo derivatives have been evaluated by using ab initio methods. The combination of the Polarizable continuum model for estimating bulk solvent effects with the TD-B3LYP/6-311+G(2d,p)//B3LYP/6-311G(d,p) level of approximation, leads to an accurate description of the wavelength of maximum absorption of indigoïds compounds. Using this procedure, we have assessed the effects of both the surroundings (solvent and solid state) and the substitution pattern. For the latter, we obtained a mean absolute deviation of only 7 nm (0.02 eV) compared to experiment, for a set of 86 molecules/solvents. [ABSTRACT FROM AUTHOR]

We have investigated theoretically the interband excitonic absorption spectra and the coupling behaviors of coupled symmetric triple Zn1-xCdxSe/ZnSe quantum wells with diluted Mn doping in the central well under external magnetic field. The results show that the magnetic field can effectively adjust the energy levels and the optical properties of the coupled multiple quantum wells (CMQWs). The coupling behaviors of the CMQWs are very sensitive to the central well depth. The effect of the magnetic-field-introduced parabolic-confined potential on the main features of the absorption spectra can be neglected at moderate magnetic-field densities. [ABSTRACT FROM AUTHOR]

We consider three distinct methods of calculating the vibronic levels and absorption spectra of molecular dimers coupled by dipole-dipole interactions. The first method is direct diagonalization of the vibronic Hamiltonian in a basis of monomer eigenstates. The second method is to use creation and annihilation operators leading in harmonic approximation to the Jaynes–Cummings Hamiltonian. The adiabatic approximation to this problem provides insight into spectral behavior in the weak and strong coupling limits. The third method, which serves as a check on the accuracy of the previous methods, is a numerically exact solution of the time-dependent Schrödinger equation. Using these methods, dimer spectra are calculated for three separate dye molecules and show good agreement with measured spectra. [ABSTRACT FROM AUTHOR]

A general formulation of nonperturbative quantum dynamics of solutes in a condensed phase is proposed to calculate linear and nonlinear vibrational line shapes. In the weak solute-solvent interaction limit, the temporal absorption profile can be approximately factorized into the population relaxation profile from the off-diagonal coupling and the pure-dephasing profile from the diagonal coupling. The strength of dissipation and the anharmonicity-induced dephasing rate are derived in Appendix A. The vibrational energy relaxation (VER) rate is negligible for slow solvent fluctuations, yet it does not justify the Markovian treatment of off-diagonal contributions to vibrational line shapes. Non-Markovian VER effects are manifested as asymmetric envelops in the temporal absorption profile, or equivalently as side bands in the frequency domain absorption spectrum. The side bands are solvent-induced multiple-photon effects which are absent in the Markovian VER treatment. Exact path integral calculations yield non-Lorentzian central peaks in absorption spectrum resulting from couplings between population relaxations of different vibrational states. These predictions cannot be reproduced by the perturbative or the Markovian approximations. For anharmonic potentials, the absorption spectrum shows asymmetric central peaks and the asymmetry increases with anharmonicity. At large anharmonicities, all the approximation schemes break down and a full nonperturbative path integral calculation that explicitly accounts for the exact VER effects is needed. A numerical analysis of the O–H stretch of HOD in D2O solvent reveals that the non-Markovian VER effects generate a small recurrence of the echo peak shift around 200 fs, which cannot be reproduced with a Markovian VER rate. In general, the nonperturbative and non-Markovian VER contributions have a stronger effect on nonlinear vibrational line shapes than on linear absorption.© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Irradiance dependence of excitonic nonlinear absorption in cadmium sulfide (CdS) nanocrystals has been studied by using Z-scan method with nanosecond laser pulses. The wavelength dependence of nonlinear absorption has also been measured near the excitonic transition of 1S(e)–1S3/2(h). We observe the saturable absorption, which can be described by a third-order and a fifth-order nonlinear process for both 3.0-nm-sized and 2.3-nm-sized CdS nanocrystals. The experimental results show that the excitonic nonlinear absorption of CdS nanocrystals is greatly enhanced with decreasing particle size. A two-level model is utilized to explain both irradiance and wavelength dependence of the excitonic nonlinearity. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The optical absorption spectra in a quantum well driven both by an intense terahertz (THz) and by an optical pulse are theoretically investigated within the theory of density matrix. We found that the optical absorption spectra and the splitting of the excitonic peaks splitting can be controlled by changing the THz field intensity and/or frequency. The Autler–Towns splitting is a result of the THz nonlinear dynamics of confined excitons, which is in agreement with the experiments. In addition, the dependence of the optical absorption on the quantum well width and the carrier density is also discussed. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A study is made of the excitonic absorption spectra of solid solutions of the system (KI)2–(1-x)AgI–xCuI. On the basis of the dependence of the parameters of the excitonic bands on the concentration x, it is established that solid solutions of the type K2Ag1-xCuxI3 are formed in the range 0≤x≤0.2. Substitution of Ag atoms by Cu atoms in the AgI42- tetrahedra, which form chains in the orthorhombic crystal K2AgI3, promotes the formation of quasi-1D exciton bands and spectra of the persistence type, according to the Onodera–Toyozawa classification, with a splitting off of the impurity band from the exciton band. Comparison with the results of studies of the excitonic spectra in solid solutions Rb2Ag1-xCuxI3 and Cs2Ag1-xCuxI3 attests to the appearance of the Rashba effect at small x and to qualitative agreement with the Onodera–Toyozawa theory. [ABSTRACT FROM AUTHOR]

We report on very high efficiency deep-blue phosphorescent organic light-emitting devices (PHOLEDs) based on iridium(III) bis(4′,6′-difluorophenylpyridinato)tetrakis(1-pyrazolyl)borate (FIr6). Dual emissive layers consisting of an N,N′-dicarbazolyl-3,5-benzene layer doped with 4 wt % FIr6 and a p-bis(triphenylsilyly)benzene layer doped with 25 wt % FIr6 were employed to maximize exciton generation on FIr6 molecules. Combined with the p-i-n device structure, we achieved a low turn-on voltage of 3.2 V and very high power efficiencies of 25±2 lm/W at 100 cd/m2 and 20±2 lm/W at 1000 cd/m2 for such deep-blue PHOLEDs with peak emission at a wavelength of 458 nm. [ABSTRACT FROM AUTHOR]

We demonstrate alpha-particle detection in an n-type 4H-SiC Schottky diode detector up to a temperature of 500 °C using an Am-241 disc source. The measured spectra were used to calculate the electron-hole pair creation energy in 4H-SiC and its non-bandgap contribution, which are both found to decrease with increasing temperature. The full width at half maximum (FWHM) of the measured alpha-energy peaks was found to increase exponentially with temperature due to an exponential increase of leakage current. For our measurement system, above 300 °C, where the leakage current was 10-6 A, this increase exceeded the FWHM at room temperature. [ABSTRACT FROM AUTHOR]

Singlet fission sensitized photovoltaics have the potential to surpass the Shockley-Queisser limit for a single-junction structure. We investigate the dynamics of triplet excitons resulting from singlet fission in pentacene and their ionization at a C60 heterojunction. We model the generation and diffusion of excitons to predict the spectral response. We find the triplet diffusion length in polycrystalline pentacene to be 40 nm. Poly(3-hexylthiophene) between the electrode and pentacene works both to confine triplet excitons and also to transfer photogenerated singlet excitons into pentacene with 30% efficiency. The lower bound for the singlet fission quantum efficiency in pentacene is 180 ± 15%. [ABSTRACT FROM AUTHOR]