Rate of radiationless electronic transitions for molecules in the condensed phase

Rate constants of radiationless electronic transitions in a diatomic molecule in a crystal at non-zero temperature are calculated. The electronic terms of the molecule are simulated by the Morse potential. The crystal vibrations are assumed to be harmonic. The calculations are done under the assumption that perturbation theory is applicable to the operator inducing the electronic transitions. The vibrational interaction of the molecule with the medium is not supposed to be small. The results explain certain experimental data on the radiationless electronic transitions in aromatic hydrocarbons.     

Non-condon scheme of radiationless transitions for the morse oscillator model

The non-adiabatic coupling matrix elements responsible for radiationless deactivation of an electronically excited molecule are calculated without invoking the Condon approximation. Assuming the Morse potential surfaces for vibrational motion along the local and totally symmetric normal coordinates, the vibronic part of the radiationless rate constant is calculated. It is shown that the rate constant in the non-Condon scheme exceeds that obtained in the Condon approximation by about two orders of magnitude. The calculated dependence of the radiationless rate constant on the energy gap is in good agreement with the experimentally observed energy gap law for intersystem crossing T₁ → S₀ rate constants in aromatic hydrocarbons.     

On the Mechanism of Magnetic Quenching of Fluorescence in Gaseous State

The pressure dependence of fluorescence quenching of gaseous glyoxal has been measured in the presence of a magnetic field of 1–8 kG. Below 5 kG both the collision free lifetime and the collisional quenching constant were found to be dependent upon magnetic field strength. Above 5 kG the Collisional quenching constant turned out to be nearly equal to the value without magnetic field and the collision free lifetime took a constant value larger than that without magnetic field. The magnetic enhancement of the intramolecular radiationless transition of gaseous molecules has been studied theoretically. The phenomenon is shown to be explained by considering two mechanisms, mechanisms I and II. Mechanism I is due to the interaction of a primary state with secondary states through the Zeeman hamiltonian. Mechanism II is due to the shift and broadening of appropriate rovibronic levels by the Zeeman effect.     

The nature of molecular excited states produced by weak light sources

It is shown that upon excitation of a molecule by light from a thermal source, the incident field tends to act as a projection operator for a subspace spanned by eigenstates of the molecular hamiltonian. Furthermore, for chaotic light sources there is an effective upper limit, τ, for the time during which there is coherent excitation. If τ is much greater than the uncertainty minimum, as is normally the case, the reduced density operator for the excited states of the molecule becomes “filtered”, the extent of which determines the pattern of subsequent radiative and radiationless decay processes. The limitation of the “filtering” process to the interval τ provides a new distinction for large- and small-molecule behavior.     

On the possibility of quantum beats in the total fluorescence of large molecules

The temporal evolution of the total emission from excited electronic states of a large molecule which corresponds to the statistical limit for radiationless relaxation is considered within the two-discrete-states model. It is shown that quantum beats in total (spectrally unresolved) emission may be revealed when the excited discrete levels differ in their rate constants for radiationless relaxation even if they have equal rate constants for radiative decay.     

Deuterium isotope effect on charge-transfer fluorescence

Quantum yields and decay times of fluorescence of charge-transfer complexes of tetracyanoethylene (an electron acceptor) with protonated and deuterated aromatic hydrocarbon donors were measured. The deuterium isotope effect on radiationless transition (identified as the

internal conversion) was observed. This observation is taken as evidence of the dominant role of intramolecular within the donor and/or the acceptor molecule) vibrations in radiationless transitions from excited charge-transfer states of molecular complexes.     

Excited electronic states and photophysics of uracil–water complexes

The electronically excited singlet states of complexes of uracil with one water molecule have been studied theoretically using ab initio multireference configuration interaction methods. In agreement with previous theoretical and experimental results, four cyclic isomers of uracil forming hydrogen bonds with the water molecule have been located with energies within 0.2 eV from the lowest energy isomer. Focus has been given on the mechanism for radiationless decay to the ground state after initial UV absorption and on the effect of complexation with water on previously reported radiationless decay pathways. Features on the excited state potential energy surfaces, such as minima, transition states and conical intersections, have been located for all isomers and compared with those of free uracil. The hydrogen-bonded water molecule changes the relative energies of these features and may lead to different excited state dynamics and lifetimes, in agreement with experimental observations.     

Inhomogeneous Electron Liquid in a Homogeneous Magnetic Field of Arbitrary Strength

Abstract

Our recent paper [Phys. Rev. A, 60, 2853 (1999)] on the field dependence of the energy of a molecule in an arbitrary magnetic field is extended here by results which can be expressed solely in terms of the total kinetic energy of the electron liquid of a molecule or an atom in a homogeneous magnetic field.     

Detailed dynamics of the nonradiative deactivation of adenine: a semiclassical dynamics study

A realistic dynamics simulation study is reported for the ultrafast radiationless deactivation of 9H-adenine. The simulation follows two different excitations induced by two 80 fs (fwhm) laser pulses that are different in energy: one has a photon energy of 5.0 eV, and the other has a photon energy of 4.8 eV. The simulation shows that the excited molecule decays to the electronic ground state from the (1)pipi* state in both excitations but through two different radiationless pathways: in the 5.0 eV excitation, the decay channel involves the out-of-plane vibration of the amino group, whereas in the 4.8 eV excitation, the decay strongly associates with the deformation of the pyrimidine at the C 2 atom. The lifetime of the (1) npi* state determined in the simulation study is 630 fs for the 5.0 eV excitation and 1120 fs for the 4.8 eV excitation. These are consistent with the experimental values of 750 and 1000 fs. We conclude that the experimentally observed difference in the lifetime of the (1) npi* state at various excitations results from the different radiationless deactivation pathways of the excited molecule to the electronic ground state.     

Excited-state dynamics of acetylene excited to individual rotational level of the V04K01 subband

Dynamics of the IR emission induced by excitation of the acetylene molecule using the (3(2)K(a) (0,1,2),A (1)A(u)<--4(1)l(a) (1),X (1)Sigma(g) (+)) transition was investigated. The observed IR emission was assigned to transitions between the ground-state vibrational levels. Acetylene fluorescence quenching induced by external electric and magnetic fields acting upon the system prepared using the (3(4)K(a) (1),A (1)A(u)<--0(0)l(a) (0),X (1)Sigma(g) (+)) excitation was also studied. External electric field creates an additional radiationless pathway to the ground-state levels, coupling levels of the A (1)A(u) excited state to the quasiresonant levels of the X (1)Sigma(g) (+) ground state. The level density of the ground state in the vicinity of the excited state is very high, thus the electric-field-induced transition is irreversible, with the rate constant described by the Fermi rule. Magnetic field alters the decay profile without changing the fluorescence quantum yield in collisionless conditions. IR emission from the CCH transient was detected, and was also affected by the external electric and magnetic fields. Acetylene predissociation was demonstrated to proceed by the direct S(1)-->S(0) mechanism. The results were explained using the previously developed theoretical approach, yielding values of the relevant model parameters.     

Theory of radiationless transitions in a crystalline host material

Consistent calculations of the rate constant of radiationless electron transition are reported for a diatomic molecule in a crystal at zero temperature. The transition between electronic states occurs due to nonadiabaticity. Relaxation of the vibrational energy is stimulated by the interaction of the molecule with the crystal. The calculations have been carried out under the assumption that perturbation theory with respect to the nonadiabaticity operator is applicable. The vibrational interaction of the molecule with the environment is assumed not to be small. The electronic terms of the molecule are approximated by Morse potentials.     

On the theory of the radical radiation formation in a solid host

The calculation of the radical formation rate constant in solid organic compounds is carried out. This formation is a result of the cleavage of the hydrogen atom from the carbon atom via a radiationless electronic transition in an electronically excited molecule. The electronic transition is supposed to be stipulated by the nonadiabaticity operator and the perturbation theory with respect to this operator is supposed to be applicable. The vibrational interaction of an electronically excited molecule with the host environment is assumed not to be small. The calculation is carried out within the framework of a model in which the whole molecule is represented by a CH group this being treated as a Morse oscillator. The specific features of the different substances in such a model are simulated by different values of the CH bond parameters.     

Magnetic quenching of fluorescence

The direct and indirect mechanisms for the magnetic enhancement of radiationless decay processes are described, and used to account for the experimental observations of the magnetic quenching of fluorescence from carbon disulphide, glyoxal, and nitrogen dioxide.     

Effective potential energy curves of H2 molecule evolving in a strong time‐dependent magnetic field

Evolution of hydrogen molecule, starting initially from its field‐free ground state, in a time‐dependent (TD) magnetic field of order 10¹¹ G is presented in a parallel internuclear axis and magnetic field‐axis configuration. Effective potential energy curves (EPECs), in terms of exchange and correlation energy, of the hydrogen molecule as a function of TD magnetic‐field strength, are analyzed through TD density functional computations based on a quantum fluid dynamics approach. The numerical computations are performed for internuclear separation R ranging from 0.1 to 14.0 a.u. The EPECs exhibit field‐dependent significant potential‐well minima both at large internuclear separations and at short internuclear separations with a considerable increase in the exchange and correlation energy of the hydrogen molecule. The results, when compared with the time‐independent (TI) studies involving static TI magnetic fields, reveal TD behavior of field‐dependent crossovers between different spin‐states of hydrogen molecule as indicated by the TI investigations in static magnetic fields. Besides this, present work reveals interesting dynamics in the TD total‐electronic charge‐density distribution of the hydrogen molecule. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Theoretical study of magnetic properties of ammonia molecule in nonuniform magnetic field

The interaction Hamiltonian within the Bloch gauge for the potentials of the electromagnetic field has been used to define magnetic multipole moment operators and operators for the magnetic field of electrons acting on the nuclei of a molecule in the presence of nonhomogeneous external magnetic field. Perturbation theory has been applied to evaluate the induced electronic moments and magnetic field at the nuclei. Multipole magnetic susceptibility and nuclear magnetic shielding tensors have been introduced to describe the contributions arising in nonuniform fields, and their origin dependence has been analyzed. Extended numerical tests on the ammonia molecule in a static, nonuniform magnetic field have been carried out, using the random-phase approximation within the framework of accurate Hartree-Fock zero-order wavefunctions, and allowing for both angular momentum and torque formalisms in the calculation of paramagnetic contributions.     

Viscosity dependent radiationless relaxation rate of cyanine dyes. A picosecond laser spectroscopy study

The viscosity dependent radiationless relaxation of several cyanine dyes has been studied by picosecond laser spectroscopy. It was found that the relaxation rate is proportional to η^?α. The value of α, however, is not constant for a certain dye molecule, but is strongly dependent on the kind of solvent used. In n-alcohols for instance α is typically about 1. In glycerol/methanol or glycerol/water mixtures on the other hand α ≈ 0.5. A comparison is made with literature data on orientational relaxation lifetimes of some dyes in similar solvents. It is shown that the radiationless relaxation of cyanine dyes and the orientational relaxation of for instance xanthene dyes changes in roughly the same way as the solvent is changed. This is taken as proof of the proposal that a torsional motion of the heterocyclic quinolyl rings is the main course of the viscosity dependent relaxation of the cyanine dyes studied.     

The photolysis of n-butyraldehyde in isooctane at 313 nm

The effects of aldehyde concentration, incident light intensity, and temperature on the quantum yields of reaction products were studied. Mechanisms for primary and secondary photochemical processes were suggested, and primary quantum yields as well as rate constant ratios were derived. Reversibility of intramolecular γ-hydrogen transfer and disproportionation of the radical pair formed in the reaction of an excited triplet and ground state molecule were shown to provide important pathways for radiationless decay of the triplet state.     

The first ionization energy of NO2. What answer can be brought at present by photoelectron spectroscopy?

Reinvestigation of the Ar 1048-1067 Å photoelectron spectrum of NO₂ using a completely NO-free sample suggests an upper limit for the adiabatic first ionization energy of this molecule consistent with the 9.75 eV photoionization value. The very low cross section process observed below 10.0 eV is interpreted by a mechanism involving autoionization followed by radiationless transition toward NO₂⁺ ionic ground state.     

Direct chiral discrimination in NMR spectroscopy

Conventional nuclear magnetic resonance spectroscopy is unable to distinguish between the two mirror-image forms (enantiomers) of a chiral molecule. This is because the NMR spectrum is determined by the chemical shifts and spin–spin coupling constants which – in the absence of a chiral solvent – are identical for the two enantiomers. We discuss how chirality may nevertheless be directly detected in liquid-state NMR spectroscopy: In a chiral molecule, the rotating nuclear magnetic moment induces an electric dipole moment in the direction perpendicular to itself and to the permanent magnetic field of the spectrometer. We present computations of the precessing electric polarization following a π/2 pulse. Our estimates indicate that the electric polarization should be detectable in favourable cases. We also predict that application of an electrostatic field induces a chirally sensitive magnetization oscillating in the direction of the permanent magnetic field. We show that the electric-field-perturbed chemical shift tensor, the nuclear magnetic shielding polarizability, underlies these chiral NMR effects.     

On the Control of Magnetic Anisotropy through an External Electric Field

The effect of an external electric field on the magnetic anisotropy of a single‐molecule magnet has been investigated, for the first time, with the help of DFT. The application of an electric field can alter the magnetic anisotropy from “easy‐plane” to “easy‐axis” type. Excitation analysis performed through time‐dependent DFT predicts that the external electric field facilitates metal to π‐acceptor ligand charge transfer, leading to uniaxial magnetic anisotropy and concomitant spin Hall effect in a single molecule.