Composite exciton-phonon states in molecular crystals

It is known that the diagonalization of the exciton-phonon Hamiltonian gives rise to the composite exciton-phonon energy states. Within the single phonon approximation, two different diagonalized Hamiltonians are obtained for 0–0 and 0–1 phonon transitions in pure molecular crystals. The resulting secular equations are solved, and analytical expressions for the energy eigenvalues corresponding to the two transitions are derived. The thermal broadening due to the composite exciton-phonon states interaction is also calculated at low temperatures, and the results agree with experiments.     

One particle CPA and exciton-phonon interactions in molecular crystals

The intersite correlation function of scattering potentials for the exciton-acoustic phonon interaction in molecular crystals is calculated. It shows a complicated dependnece on the intersite distance and the temperature. The existence of such cross correlation clearly points out that one has to go beyond the one particle CPA in order to treat properly the problem of exciton-delocalized phonon interactions.     

Reclassifying exciton-phonon coupling in molecular aggregates: evidence of strong nonadiabatic coupling in oligothiophene crystals

Exciton-phonon (EP) coupling in molecular aggregates is reexamined in cases where extended intermolecular interactions result in low-energy excitons with high effective masses. The analysis is based on a single intramolecular vibrational mode with frequency omega0 and Huang-Rhys factor lambda2. When the curvature Jc at the exciton band bottom is much smaller than the free-exciton Davydov splitting W, the strength of the EP coupling is determined by comparing the nuclear relaxation energy lambda2omega0 with the curvature. In this way, weak (lambda2omega0<4piJc), intermediate I (lambda2omega0 approximately 4piJc), and strong I (lambda2omega0>4piJc) coupling regimes are introduced. The conventional intermediate (lambda2omega0 approximately W) and strong (lambda2omega0>W) EP coupling regimes originally defined by Simpson and Peterson [J. Chem. Phys. 26, 588 (1957)] are based solely on the Davydov splitting and are referred to here as intermediate II and strong II regimes, respectively. Within the intermediate I and strong I regimes the near degeneracy of the low-energy excitons allows efficient nonadiabatic coupling, resulting in a spectral splitting between the b- and ac-polarized first replicas in the vibronic progression characterizing optical absorption. Such spectral signatures are clearly observed in OT4 thin films and crystals, where splittings for the lowest energy mode with omega0=161 cm(-1) are as large as 30 cm(-1) with a small variation due to sample disorder. Numerical calculations using a multiphonon BO basis set and a Hamiltonian including linear EP coupling yield excellent agreement with experiment.     

High frequency excitations in a molecular glass

Neutron inelastic triple-axis spectra of CD₃OD/6%D₂O in the glassy and liquid phases are reported. Both the dispersion and damping of the sound modes show characteristic features as the temperature is lowered to the glassy regime. Furthermore, analysis of the observed scattering intensities reveals the presence in the glass of a second component centred at zero frequency which is not observed in the liquid.     

Excavations in molecular crystals

Single crystals built from porous molecular networks can react with agents that penetrate the crystals, cleave fragments from the network, and thereby increase the volume available for guests, all without loss of crystallinity.     

Analogy between real irreducible tensor operator and molecular two-particle operator

. Molecular matrix elements of a physical operator are expanded in terms of polycentric matrix elements in the atomic basis by multiplying each by a geometrical factor. The number of terms in the expansion can be minimized by using molecular symmetry. We have shown that irreducible tensor operators can be used to imitate the actual physical operators. The matrix elements of irreducible tensor operators are easily computed by choosing rational irreducible tensor operators and irreducible bases. A set of geometrical factors generated from the expansion of the matrix elements of irreducible tensor operator can be transferred to the expansion of the matrix elements of the physical operator to compute the molecular matrix elements of the physical operator. Two scalar product operators are employed to simulate molecular two-particle operators. Thus two equivalent approaches to generating the geometrical factors are provided, where real irreducible tensor sets with real bases are used. Received: 3 September 1996 / Accepted: 19 December 1996     

Some effects of structural disorder on the optical properties of organic molecular crystals

We investigate the effects of structural disorder on the absorption line shapes of the lowest exciton states in molecular crystals at zero temperature by the application of the average t-matrix approximation to a system characterized by a gaussian distribution of site excitation energies. The line shape exhibits asymmetric line broadening with the high energy portion being close to lorentzian, while the low energy edge is sharp. The energy dependence of the low energy tail is determined by the dimensionality of the exciton band structure.     

Laser control of molecular excitations in stochastic dissipative media

In the present work, ideas for controlling photochemical reactions in dissipative environments using shaped laser pulses are presented. New time-local control algorithms for the stochastic Schro?dinger equation are introduced and compared to their reduced density matrix analog. The numerical schemes rely on time-dependent targets for guiding the reaction along a preferred path. The methods are tested on the vibrational control of adsorbates at metallic surfaces and on the ultrafast electron dynamics in a strong dissipative medium. The selective excitation of the specific states is achieved with improved yield when using the new algorithms. Both methods exhibit similar convergence behavior and results compare well with those obtained using local optimal control for the reduced density matrix. The favorable scaling of the methods allows to tackle larger systems and to control photochemical reactions in dissipative media of molecules with many more degrees of freedom.     

New excimers in molecular crystals

A method of forming new excimeric systems is presented. We use a host crystal with pair structure to induce the excimeric configuration on the guest molecules. The emission and decay times of anthracene derivatives substituted in 9 and 9.10 positions in pyrene are studied. Excimers are formed in all the mixed crystals considered, including dimethyl anthracene which does not form excimers in its pure crystal.     

Rotational effects in molecular crystals

The Mössbauer spectrum of ferric oxinate exhibits and asymmetric quadrupole doublet. The modification of the dynamic Mössbauer parameters (to the equal values for each line) following the irradiation, was explained by the internal oxine ligands rotation inside of the octahedral coordination.     

Examination of stabilty of molecular agglomerates in molecular crystals

We report an examination algorithm of stability of molecular aggregates based on the estimation of rigidity of intermolecular contacts in a crystal structure. The algorithm includes the intermolecular interaction energy calculation (in the atom-atom potential approximation) of a pair of molecules selected in the crystal structure. Further, the energy is minimized using a least-squares technique by varying the position and orientation of one of the molecules. The contact rigidity is quantitatively assessed by the minimized rms difference between the positions of the atoms in the original and optimized structures (Zorkii’s criterion). Every rigid contact revealed in the structure determines finite or infinite stable agglomerates. The paper presents the results of testing the computer program based on this algorithm with a number of real crystal structures previously determined by single crystal X-ray diffraction, and also the examples of the most common stable molecular agglomerates found with the aid of the program.     

Sonofragmentation of molecular crystals

Possible mechanisms for the breakage of molecular crystals under high-intensity ultrasound were investigated using acetylsalicylic acid (aspirin) crystals as a model compound for active pharmaceutical ingredients. Surprisingly, kinetics experiments ruled out particle-particle collisions as a viable mechanism for sonofragmentation. Two other possible mechanisms (particle-horn and particle-wall collisions) were dismissed on the basis of decoupling experiments. Direct particle-shock wave interactions are therefore indicated as the primary mechanism of sonofragmentation of molecular crystals.     

Polarization effects in molecular crystals

A simple model of a molecular crystal is used to resolve apparent inconsistencies between existing approaches applied in calculations of polarization energies on the one hand and charge-transfer integrals on the other.     

Perturbations of molecular extravalence excitations by rare-gas fluids

In this paper we report the results of an experimental study of the vacuum ultraviolet absorption spectra of molecular impurity states of methyl iodide in Ar (density range ? = 0–1.4 g cm^?3) and in Kr (? = 0–2.3 g cm^?3), of carbon disulphide in Ar (? = 0–1.4 g cm^?3) and of formaldehyde in Ar (? = 0–1.25 g cm^?3). The experimental results provide new information regarding medium perturbations of intravalenc transitions, of the lowest extravalence transitions and of transitions to mixed valence—Rydberg configurations, which serve as a diagnostic tool to distinguish between different types of electronic excitations. All the lowest extravalence molecular excitations exhibit appreciable blue spectral shifts at moderate and at high fluid densities, intravalence transitions are practically insensitive to medium effects, while excitations to mixed valence—Rydberg configurations are characterized by a moderate blue spectral shift. New information has been obtained concerning the energetics of molecular ionization processes in a dense fluid. The high n = 2–5 Rydberg states of CH₃l exhibit a large red shift at moderate (? = 0–0.5 cm^?3) Ar densities. The ionization potential E_g and the effective Rydberg constant G for CH₃I in Ar was found to decrease from G = 13.6 eV and E_g = 9.55 eV at ? = 0 and E_g = 9.08 eV and constant G for CH₃l in Ar was found to decrease from G = 13.6 eV and E_g = 9.55eV at ? = 0 and E_g = 9.08 eV and G ≈ 7.15 eV at ? = 0.5 g cm^?3. Experimental evidence was obtained for the identification of n = 2 molecular Wannier impurity states of CH₃I and of CH₂O in liquid Ar. These spectroscopic data result in E_g ≈ 8.6 eV for CH₃I in liquid Ar and E_g ≈ 10.2 eV for CH₂O in liquid Ar.     

Cooperative exciton spectra in molecular crystals

It is shown that the singlet exciton spectrum in the crystal is coupled with that of the two-particle excitations (singlet, triplet excitons, magnons, triplet exciton-magnon). Splitting on the excitation spectrum occurs when the composite energy of the two-particle excitations is close to that of the singlet exciton.     

Mechanical mixing of molecular crystals

Supramolecular reactions between crystalline materials can be exploited to prepare both hydrogen bonded co-crystals and coordination networks. Mechanical mixing of molecular crystals as well as kneading provide an alternative, solvent-free, route to novel materials hence these methods represent a green route to supramolecular solid-state chemistry.     

Biexciton spectra of molecular crystals

A theory on the formation of biexcitons in the UV region of frequencies of molecular cyrstals is developed by considering exciton-exciton interactions. The spectral function for the biexciton spectrum is derived and conditions for the existence of bound biexciton states are established. The possibility of configuration mixing between biexciton and singlet exciton states is discussed.