Direct Visual Evidence for Neutral and Charged Hexaphyrin Aromaticity with and without Keto-Defect

We use density functional theory and time-dependent together with a set of extensive mul- tidimensional visualization techniques to characterize the influence of keto effect on charge distribution at ground state and electronic transitions for neutral and charged hexaphyrin aromaticity with and without keto-defect. It is found that the aromaticity is the key fac- tor to influence the ground state Mulliken charges distribution properties, other than the meso-aryl-substituted effect. But with the enhancement of the keto-defect, the distribution changes of Mulliken charges on the hexaphyrin groups are larger than those on the pentaflu- orophenyl substituted groups, following with the aromaticity changes from nonaromatic to aromatic. Furthermore, through characterizing by transition density and charge difference density, direct visual evidence for neutral and charged aromaticity with and without keto- defect can be clearly derived, and the ability of charge transfer between units of monoradical （nonaromaticity） and singlet biradical （aromaticity） forms is much stronger than that of neutral forms.

Kramers–Henneberger Form of Strong Field Theory with the Correction of Dipole Approximation

We show that the breakdown of dipole approximation can be adopted to explain the asymmetry structure in the photoelectron momentum distributions along the beam propagation direction, which is defined as the photoelectron longitudinal momentum distributions（PLMD）, in tunneling regime（K ？ 1）, based on the strong field approximation theory. The nondipole Hamiltonian for photoelectrons interacting with laser fields from a hydrogen-like atom is transformed into the Kramers–Henneberger frame in our model. To introduce the correction of dipole approximation, the spatial variable is kept in a vector potential （r, t）, demonstrating that the breakdown of dipole approximation is the major reason for the shift of the peak in PLMD. The nondipole effects are apparent when circularly polarized lasers are adopted to ionize the atoms, and clear tendency to increase offsets is found for increasing laser intensities.

∧-related Quantum Interference of ^2П [Case（a）] Diatom on Rotational Energy Transfer

To study theoretically the relationship between the integral interference angle and the scat- tering angle in collisional quantum interference, the integral interference angle of atom- ^2П[case（a）] diatomic molecules system is described. To simulate the experiment theoretically, the theoretical model on collision-induced rotational energy transfer in an atom- ^2П[case（a）]diatom system is presented based on the first order Born approximation taking into account of the long-range interaction potential. For the ^2П electronic state in the Hund＇s case（a） diatom, the degree of the interference is discussed. The interference angles of collision-induced rotational energy transfer of CN（A^2П） in Hund＇s case（a） with He, Ne, and Ar are calculated quantitatively. The key parameters in the determination of integral interference angles are obtained.

Filling gap of combination of gauge and analytical method in KFR-like theory

Bauer recently presented a formula for the ionization rate of a hydrogen atom in a strong linearly polarized laser field[J.Phys.B 49145601(2016)].He started from the Keldysh probability amplitude in the length gauge and utilized Reiss’s method in the velocity gauge.Instead,according to the Reiss probability amplitude in the velocity gauge and Keldysh’s derivation for the length gauge,we derive a formula for the ionization rate of a ground-state hydrogen atom or a hydrogenlike atom in a strong linearly polarized laser field.We compare the numerical results of the total ionization rate and the photoelectron energy distribution calculated from our formula with the results from Keldysh,Reiss,and Bauer.We find that the apparent discrepancies in the ionization rate are caused not only by different gauges,but also by different analytical methods used to derive the ionization rate.

Photoinduced Intramolecular Charge Transfer in Donor-acceptor Dyad and Donor-bridge-acceptor Triad

The ground and excited state properties of the [60]fullerene, diphenylbenzothiadiazole-triphenylamine （PBTDP-TPA） dyad and fullerene-diphenylbenzothiadiazole-triphenylamine （fullerene-PBTDP-TPA） triad were investigated theoretically using density functional theory with B3LYP functional and 3-21G basis set and time-dependent density functional theory with B3LYP functional and STO-3G basis set as well as 2D and 3D real space analysis methods. The 2D site representation reveals the electron-hole coherence on excitation. The 3D transition density shows the orientation and strength of the transition dipole moment, and the 3D charge difference density gives the orientation and result of the intramolecular charge transfer. Also photoinduced intermolecular charge transfer （ICT） in PBTDP-TPA-fullerene triad are identified with 2D and 3D representations, which reveals the mechanisms of ICT in donor-bridge-acceptor triad on excitation. Besides that we also found that the direct superexchange ICT from donor to acceptor （tunneling through the bridge） strongly promotes the ICT in the donor-bridge-acceptor triad.

Charge and Energy Transfer in the Metal-free Indoline Dyes for Dye-sensitized Solar Cells

Metal-free indoline dyes for dye-sensitized solar cells were studied by employing quantum chemistry methods. Comparative study of the properties of both ground and excited states of metal-free indoline dyes for dye-sensitized solar cells revealed： （i） as the number of rhodanine rings increases, the energy difference between HOMO and LUMO decreases and there is a red shift in the absorption spectrum with the binding energy increased, and the transition dipole moment decreased; （ii） Based on an analysis of charge differential density, we observed that the charge and energy are transfered from the phenylethenyl to the indoline and rhodanine rings; （iii） The electron-hole coherences are mainly on the indoline and rhodanine rings, and the exciton sizes are 30 and 40 atoms for indoline dyes with one and two rhodanline rings, respectively. These results serve as a good example of computer-aided design in metal-free indoline dyes for dye-sensitized solar cells.

Time-Dependent Quantum Wave Packet Calculation for Reaction S-(^(2)P)+H_(2)(^(1)∑_(g)^(+))→SH-(^(1)∑)+H(^(2)S) on Ab Initio Potential Energy Surface

The time-dependent wave packet propagation method was applied to investigate the dynamic behaviours of the reaction S-(^(2)P)+H_(2)(^(1)∑_(g)^(+))→SH-(^(1)∑)+H(^(2)S)based on the electronic ground state(^(2)A′)potential energy surface of the SH_(2)-ionic molecule.The collision energy dependent reaction probabilities and integral cross sections are obtained.The numerical results suggest that there are significant oscillation structures over all the studied range of the collision energies.The vibrational excitation and rotational excitation of the diatomic reagent H_(2) promote the reactivity significantly as suggested by the numerical total reaction probabilities with the initial rotational quantum number of j=0,2,4,6,8,10,and the vibrational quantum number v=0,1,2,3,4.The numerical integral cross sections are quite consistent with the experimental data reported in previous work.

Collision-induced Rotational Energy Transfer in an Atom-Diatom System

As a further theoretical study of the collision-induced quantum interference on rotational energy transfer in an atom-diatom system, based on the first-Born approximation of time-dependent perturbation theory, taking into account the anisotropic Lennard-Jones interaction potential and the long-range interaction potential, the differential interference angles in singlet-triplet mixed states of CO A^1Π（v=9）-e3∑-（v=1） system in collision with He, Ne, Ar, and other partners were calculated theoretically. The relationships of differential interference angle versus impact parameters, including collision parameter b and velocity, are obtained.

Transition Dipole, Charge Transfer, and Electron-hole Coherence in Two-photon Absorption： Visualizations with Two Dimensional Site and Three Dimensional Cube Representations

The developed visualization methods of two dimensional （2D） site and three dimensional （3D） cube representations have been performed to show the orientation of transition dipole, charge transfer, and electron-hole coherence in two-photon absorption （TPA）. The 3D cube representations of transition density can reveal visually the orientation and strength of transition dipole moment, and charge different density show the orientation of charge transfer in TPA. The 2D site representation can reveal visually the electron-hole coherence in TPA. The combination of 2D site and 3D cube representations provide clearly inspect into the charge transfer process and the contribution of excited molecular segments for TPA.

Ionization in an intense field considering Coulomb correction

We derive a simple ionization rate formula for the ground state of a hydrogen atom in the velocity gauge under the conditions：ω〈〈1 a.u.（a.u.is short for atomic unit） and γ〈〈1（ω is the laser frequency and y is the Keldysh parameter）.Comparisons are made among the different versions of the Keldysh-Faisal-Reiss（KFR） theory.The numerical study shows that with considering the quasi-classical（WKB） Coulomb correction in the final state of the ionized electron,the photoionization rate is enhanced compared with without considering the Coulomb correction,and the Reiss theory with the WKB Coulomb correction gives the correct result in the tunneling regime.Our concise formula of the ionization rate may provide an insight into the ionization mechanism for the ground state of a hydrogen atom.