Estimate Of Excitation Energy Research Articles

NBO/NRT Two-State Theory of Bond-Shift Spectral Excitation.

We show that natural bond orbital (NBO) and natural resonance theory (NRT) analysis methods provide both optimized Lewis-structural bonding descriptors for ground-state electronic properties as well as suitable building blocks for idealized “diabatic” two-state models of the associated spectroscopic excitations. Specifically, in the framework of single-determinant Hartree-Fock or density functional methods for a resonance-stabilized molecule or supramolecular complex, we employ NBO/NRT descriptors of the ground-state determinant to develop a qualitative picture of the associated charge-transfer excitation that dominates the valence region of the electronic spectrum. We illustrate the procedure for the elementary bond shifts of SN2-type halide exchange reaction as well as the more complex bond shifts in a series of conjugated cyanine dyes. In each case, we show how NBO-based descriptors of resonance-type 3-center, 4-electron (3c/4e) interactions provide simple estimates of spectroscopic excitation energy, bond orders, and other vibronic details of the excited-state PES that anticipate important features of the full multi-configuration description. The deep 3c/4e connections to measurable spectral properties also provide evidence for NBO-based estimates of ground-state donor-acceptor stabilization energies (sometimes criticized as “too large” compared to alternative analysis methods) that are also found to be of proper magnitude to provide useful estimates of excitation energies and structure-dependent spectral shifts.

ENERGY DISSIPATION IN FUSION REACTIONS FROM DYNAMICAL MEAN-FIELD THEORY

Nucleus-nucleus interaction potentials and friction coefficients associated with one-body energy dissipation in the entrance channel of fusion reactions are extracted from the microscopic time-dependent Hartree-Fock theory. They show center-of-mass energy dependence close to the Coulomb barrier energy. This dependence indicates dynamical reorganization of internal degrees of freedom. We give a simple estimate of excitation energy from microscopic nucleon exchange.

Performance of time-dependent density functional and Green functions methods for calculations of excitation energies in radicals and for Rydberg electronic states.

Time-dependent density functional (TD-DFT) and perturbation theory-based outer valence Green functions (OVGF) methods have been tested for calculations of excitation energies for a set of radicals, molecules, and model clusters simulating points defects in silica. The results show that the TD-DFT approach may give unreliable results not only for diffuse Rydberg states, but also for electronic states involving transitions between MOs localized in two remote from each other spatial regions, for example, for charge-transfer excitations. For the. O-SiX(3) clusters, where X is a single-valence group, TD-DFT predicts reasonable excitation energies but incorrect sequence of electronic transitions. For a number of cases where TD-DFT is shown to be unreliable, the OVGF approach can provide better estimates of excitation energies, but this method also is not expected to perform universally well. The OVGF performance is demonstrated to be satisfactory for excitations with predominantly single-determinant wave functions where the deviations of the calculated energies from experiment should not exceed 0.1-0.3 eV. However, for more complicated transitions involving multiple bonds or for excited states with multireference wave functions the OVGF approach is less reliable and error in the computed energies can reach 0.5-1 eV.

Unified quantum mechanical picture for confined spinons in dimerized and frustrated spin chains

: A quantum mechanical picture is presented to describe the behavior of confined spinons in a variety of S =1/2 chains. The confinement is due to dimerization and frustration and it manifests itself as a nonlinear potential , centered at chain ends () or produced by modulation kinks (b > 1). The calculation extends to weak or zero frustration some previous ideas valid for spinons in strongly frustrated spin chains. The local magnetization patterns of the confined spinons are calculated. A (minimum) enhancement of the local moments of about 11/3 over a single S =1/2 is found. Estimates for excitation energies and binding lengths are obtained.

Screened potential in π-electron systems and its application to the estimation of excitation energies

A diagrammatic technique was developed for the estimation of the screened potential of π-electron systems. The screened potential was expanded in terms of the polarization propagators which were constructed from either the singlet,\(\hat \Gamma ^1 \), or triplet vertex part,\(\hat \Gamma ^3 \). These vertex parts correspond to the singlet or triplet excitations, respectively, in the Random Phase Approximation (RPA) containing exchange diagrams. The excitation energies were calculated by using the screened potential in the framework of RPA with exchange. The excitation energies of several conjugated molecules with or without a hetero atom are in agreement with the experimental data.

Screened potential in π-electron systems and its application to the estimation of excitation energies

Screened potential in π-electron systems and its application to the estimation of excitation energies