One-photon Absorption Processes Research Articles

Effect of terminal substituents on intramolecular charge transfer in one- and two-photon absorption of zinc phthalocyanine derivatives

Zinc phthalocyanine derivatives have unique structure and photophysical properties, which make them a remarkable potential in the fields of optoelectronics as well as biomedicine. In order to reveal the effect of the terminal substituents on the electron transition mechanisms, one-photon absorption (OPA) and two-photon absorption (TPA) processes of three zinc phthalocyanines modified with different terminal substituents (PcZn-0, PcZn-1 and PcZn-2) have been analyzed by using density-functional theory (DFT) in combination with the sum-over-states (SOS) model, the visualization of the transition density matrix (TDM) as well as charge density difference (CDD) calculations. Red-shifted OPA absorption peaks with enhanced intensities, have been observed in molecules PcZn-1, PcZn-2 with long terminal substituents. However, for TPA process, a more effective charge transfer over almost the entire molecule has been observed in PcZn-1 molecule with 4-methoxybenonic acid as terminal substituents. When H-atoms in the hydroxyl groups of four terminal 4-Methoxybenzoic acid groups were substituted by dispersed red-one chains, a limited range of intramolecular charge transfer and localized excitation inside the dispersed red-one chain were observed, leading to a localized excitation absorption peak and expanding the wavelength region of TPA response. Furthermore, terminal substituents with conjugated branches exhibit a stronger cooperative effect between the terminal chains and shows larger TPA response. On the contrary, excessive dihedral angles between different groups can weaken the conjugation degree of molecules and affect intramolecular charge transfer as well as TPA response.

Tuning the linear optical properties and two-photon absorption on the cinnamylideneacetophenone derivatives: The effect of methoxy group by a experimental and theoretical point of view

The present work studied the effect of the methoxy group position in two cinnamylideneacetophenone (CA) derivatives on both one-photon (1PA) and two-photon absorption (2PA) processes. Our outcomes exhibit a dependence on the methoxy group position spectrally and in magnitude for both. A decrease in the lower energy 1PA band of 0.23eV was observed when the methoxy group was moved to the more conjugated part of the cinnamaldehyde molecule. The opposite was also observed for the next higher absorption band. The Quantum Chemical Calculations (QCCs), besides a good agreement between the experimental and simulated 1PA spectra, except for the magnitude of the high energy absorption band, showed that the effect behind the observed experimental red-shift of the lower absorption band is caused by the higher charge transfer when the methoxy group is bounded to the longer conjugated part of the cinnamaldehyde derivative. For experimental 2PA spectra, the higher energy band is strongly affected by the presence of the methoxy group, pointing out an increase of about 56 % in the values of the two-photon absorption cross-section (2PACS). Furthermore, the phenomenological Sum-Over-Essential States (SOS) approach and QCCs were performed for further clarification in the 2PACS experimental results. Hence, our findings demonstrate that changing the methoxy position on opposite sides of the CA may open up a novel insight for designing new organic molecules, particularly when seeking to enhance the values of 2PACS significantly of CA derivatives.

Theoretical study on photoinduced charge transfer in one-photon and two-photon absorption of branching oligofluorenes

Oligofluorenes have been identified as very promising two-photon absorption (TPA) materials and present great application potential for the fabrication of nonlinear optical devices, but the TPA mechanism and corresponding electron excitation properties have not been studied. Here, the photoinduced charge transfer characteristics of V-shaped and Y-shaped branching oligofluorenes that consist of two and three fluorene units in each branch during one-photon absorption (OPA) and TPA processes are analyzed theoretically using the density functional theory and visualization sum-over-states model. The calculated results show that the OPA intensity and TPA cross-section are significantly enhanced by increasing the branch length or changing the structure from V-shaped to Y-shaped. The long-distance charge transfer only occurs on the second transition of TPA at high excited states. Compared to Y-shaped molecules, V-shaped structures exhibit a stronger cooperative effect among the different branches.

Multifunctional Characteristics of BCTH:0.5% Sm3+ Ceramics Prepared via Hydrothermal Method and Powder Injection Molding

Briefly, 0.005-mol Sm3+-doped (Ba0.85Ca0.15)(Ti0.9Hf0.1)O3 ([(Ba0.85Ca0.15)0.995Sm0.005](Ti0.9Hf0.1)O3, BCTH:0.005Sm3+) lead-free ceramics were prepared via hydrothermal method and powder injection molding using paraffin and oleic acid as binders, and the effects of preparation method and sintering conditions on microstructure, dielectric behavior and optical properties were investigated. XRD Rietveld refinement reveals the coexistence of orthogonal, rhombohedral and tetragonal phases, in which the crystal structure and phase fraction are influenced greatly by sintering temperature and holding time. The ceramics present enhanced relaxor behavior and frequency dispersion phenomenon as compared with those prepared by the solid-state sintering method, and the diffusive index γ value is within 1.421–1.673. The transition mechanism and luminescence performance of BCTH:0.005 Sm3+ were analyzed by Blasse formula, photoluminescence spectrum and fluorescence lifetimes, where emission peaks show slight blueshift, fluorescence decay lifetime becomes shorter, electric multipole interaction dominates the energy transfer mechanism, and the down-conversion luminescence is one-photon absorption process. The CIE chromaticity color coordinate (0.4746, 0.5048), correlated color temperature 3134 K and color purity 93.58% are achieved, which reveals that the BCTH:0.005 Sm3+ ceramics express high quality yellow emission rather than orange-red light of the hydrothermal method synthesized nano-powder, and have potential application in optical field.

Enhanced Femtosecond Nonlinearities and Multiphoton Absorptions in Discrete Bands of Porphyrins.

Optical nonlinearities of discrete absorption energy levels of one of the typical heterocyclic aromatic molecules, free-base porphyrins, have been probed over a broad spectral region (400-1600 nm) utilizing intense femtosecond pulses. A wide range of strong one- and multiphoton-induced nonlinear absorptions of both the blue-end Soret (B) band (au → b1g) and red-end orbital mixing split quasi-allowed Q-bands (Qx(0,0; 0,1), Qy(0,0; 0,1), au → eg) are critically probed and reported. During the resonant excitation within B- (400 nm) and Q-bands (600-750 nm), the nonlinear absorption has become predominant by the saturation of absorption (SA) of the one-photon absorption (1PA) process due to ground-state bleaching. At nonresonant wavelengths, it is dominated by the reverse saturation of absorption (RSA), involving various nonlinear processes of two-, three-, and four-photon (2PA, 3PA, and 4PA) absorptions, either to B- or Q-bands (1100-1600 nm). The laser intensity-dependent nonresonant (2PA, 800 nm) excitations for the prominent B-band show a distinct cross-over from SA to RSA, contributed by the excited-state absorption (ESA) utilizing a three-photon induced (3PA) process, whereas resonant (1PA, 400 nm) excitation reveals a systematic strong SA process. Both wavelength- and intensity-dependent nonlinear refractive index studies exhibit positive electronic Kerr-based self-focusing effects, with prominent contributions of nonlinear absorption and higher-order effects. The spectrally discrete, highly intense laser probing of individual energy bands and the consequent variety of nonlinearities can be broadly generalized for many free-base porphyrins and metalloporphyrins. The present studies provide a strong foundation and new insight into the broad categories of macrocycles, such as porphyrins and phthalocyanines, for myriad applications in nonlinear optics and bio/optophotonics.

Reaction dynamics of molecules in highly electronically excited states attained by multiphoton and multiple excitation methods

Abstract Multiphoton absorption and multiple excitation can lead to the formation of highly electronically excited states of molecules. We have been applying these excitation methods to explore specific photochemical reactions, which are rather difficult to attain by normal one-photon absorption processes. In the present review, we will introduce several examples of these photochemical responses specific to highly excited state in the condensed phase, such as two-photon-gated cycloreversion, one-color control of both reactions in photochromic systems and rapid capture of an electron ejected from the higher excited state leading to rapid generation of charge-separated states at the high energy level with a lifetime much longer than microseconds.

Influence of nitro group on solvatochromism, nonlinear optical properties of 3-morpholinobenzanthrone: Experimental and theoretical study

We report the synthesis of 3-morpholino-9-nitrobenzanthrone (NMB) dye. By using FT-IR, 1H NMR, and X-ray crystallography, we characterized the molecular structure of the synthesized dye. The structural features of the dye were compared to those of an identical dye without nitro substituents. The push pull kind of benzanthrone dye (NMB) was examined for solvent-dependent photophysical properties. NMB exhibits a large Stokes shift. The polarity plots indicate that hydrogen-bonding interactions are influential in most of the solvents. Detailed structural analysis as well as one-photon absorption and emission process was computationally investigated for both the molecules. NMB exhibits significant two photon absorption (TPA) activity at various electron transitions ranging from visible to NIR regions. Further, Nonlinear absorption coefficient was calculated for the dye samples from the open aperture Z-scan data. The nonlinear absorption coefficient values were obtained for the dye samples for input laser pulse energies ranging from 5 to 20 µJ. The results decipher that these dye samples are prospective contenders for the fabrication of optical limiter devices. Nitro substituents at the active site enhance charge transfer, thereby enhancing the NLO response.

Super-Exchange Charge Transfer in One-Photon and Two-Photon Absorption of Multibranched Compounds

In this work, density functional theory is used to study organic molecules in a donor–acceptor (D–A) system centered on phenothiazine with strip and trigonal structures. The transition modes of the one-photon absorption (OPA) and two-photon absorption (TPA) processes of the two molecules are studied. The calculations show that the molar absorption coefficient of OPA for trigonal molecule TPPO and the cross section of TPA are both larger than those for strip molecule M1 due to the increase in the number of branches of the system. A special local excitation-enhanced charge-transfer excitation appears in strip-type molecule M1. In the charge-transfer process of trigonal D–A structure molecule TPPO, there are not only local excitation-enhanced charge-transfer excitation but also super-exchange charge transfer between the three branches that occurs due to the increase in the planarity of the system.

Phonon-assisted cyclotron resonance in Pöschl-Teller quantum well

The phonon-assisted cyclotron-resonance (PACR) effect due to the one-photon (1P) and two-photon (2P) absorption processes in a quantum well (QW) with the Pöschl-Teller (PT) potential is studied. The magneto-optical absorption coefficient as functions of photon energy for different QW-parameters, magnetic fields, and temperatures is presented. The calculations are done for four different possible cases: both 1P- and 2P-processes as well as both phonon emission and absorption processes. The numerical results for a GaAs, InAs, InSb, and GaSb PT-QW show that the PACR peaks are blueshifted with κ and magnetic field, redshifted with QW-length, but remained unchanged with temperature. Peak intensities are found to increase with κ and magnetic field and decrease with QW-length but have a complex dependency on the temperature. The full-width at half-maximum is found to increase with κ, magnetic field, and temperature but found to decrease with QW-length. The phonon emission process is always dominant in comparison with absorption. The 2P-process is comparable with the 1P-process and should be taken into account when studying the PACR in QWs.

Manipulating dynamical Rabi-splitting with two-color laser pulses.

We theoretically investigate strong-field ionization of hydrogen atoms by orthogonally polarized two-color (OTC) laser pulses consisting of a fundamental field that is resonant with the 1s - 2p transition and its second harmonic. Numerical simulations are performed by solving the two-dimensional time-dependent Schrödinger equation and recording the photoelectron momentum distribution. In this strong-field resonant ionization, the atom undergoes many Rabi cycles and the electron can be emitted within a completed Rabi-cycle leading to the splitting of the localized momentum distribution. Here, the splitting is attributed to dynamic Rabi-splitting as a result of the dynamic Stark effect. The employed OTC scheme is shown to be efficient for controlling the dynamic Rabi-splitting through the control of quantum-path interferences involved in one-photon and two-photon absorption processes. The control scheme is accomplished by varying the relative ratio intensity and optical phase between the two pulses, and its footprint is mapped in the momentum distribution. This is shown to lead to an asymmetric distribution and suppression of the ionization process. The obtained results suggest the OTC scheme as a tool for coherent control of dynamic Rabi-oscillations via the controlled quantum-path interferences, thus opening new directions towards designing quantum states via the control OTC scheme.

Cross-section determination for one- and two-photon absorption of cobalt at hard-x-ray energies

For incident x-ray energies below the core level ionization threshold, one-photon absorption (OPA) leads to off-resonant x-ray excitations that are mediated by a virtual intermediate electronic state. In the linear regime of x-ray interaction, this intermediate state may decay radiatively and the maximum energy of the emitted photon is given by the initial and final atomic state as well as the energy of the incident photon. In the nonlinear excitation regime, however, this intermediate state may be depleted by a second x-ray absorption process as described in the sequential two-photon absorption (TPA) mechanism. Since the same intermediate state is involved in the OPA and TPA processes, the cross-section values for OPA and TPA are interconnected. We report on the determination of cross-section values for off-resonant excitation conditions, and show how the data can be used for estimating the TPA cross section in the sequential absorption mechanism. The determined off-resonant cross sections for cobalt exhibit a Lorentz-like energy-dependent behavior allowing for an energy-dependent description of the OPA and TPA cross sections with semiempirical models. The dependence of TPA cross sections on atomic number is discussed and different scaling laws are investigated. The effect of the lifetimes of a virtual intermediate state is also studied in relation to the incidence x-ray energy.

State-Population Narrowing Effect in Two-Photon Absorption for Intense Hard X-ray Pulses

We report on studies of state-populations during the two-photon absorption process using intense X-ray pulses. The calculations were performed in a time-dependent manner using a simple three-level model expressed by coupled rate equations. We show that the proposed approach describes well the measured rates of X-rays excited in the one-photon and two-photon absorption processes, and allows detailed investigation of the state population dynamics during the course of the incident X-ray pulse. Finally, we demonstrate that the nonlinear interaction of X-ray pulses with atoms leads to a time-narrowing of state populations. This narrowing-effect is attributed to a quadratic incidence X-ray intensity dependence characteristic for nonlinear interactions of photons with matter.

Photoexcitation mechanisms of new D-π-A coumarin derivatives in linear and nonlinear optical processes

Linear and nonlinear optical properties (NLO) of two donor-bridge-acceptor (D-π-A) coumarin derivatives as nonlinear optical materials were theoretically simulated using the density functional theory and time-dependent density functional theory methods. Three models were employed to study the one-photon absorption process, and the polarizable continuum model have shown better results. Visualized methods, the charge difference density and transition density matrix, were presented and have revealed intramolecular charge transfer mechanisms. The static electric field, the first hyperpolarizability and two-photon absorption (TPA) cross section were calculated, which show strong NLO effects and large TPA cross sections. In general, our results demonstrated good accordance with the experimental reports.

One-step fabrication of submicrostructures by low one-photon absorption direct laser writing technique with local thermal effect

In this work, local thermal effect induced by a continuous-wave laser has been investigated and exploited to optimize the low one-photon absorption (LOPA) direct laser writing (DLW) technique for fabrication of polymer-based microstructures. It was demonstrated that the temperature of excited SU8 photoresist at the focusing area increases to above 100 °C due to high excitation intensity and becomes stable at that temperature thanks to the use of a continuous-wave laser at 532 nm-wavelength. This optically induced thermal effect immediately completes the crosslinking process at the photopolymerized region, allowing obtain desired structures without using the conventional post-exposure bake (PEB) step, which is usually realized after the exposure. Theoretical calculation of the temperature distribution induced by local optical excitation using finite element method confirmed the experimental results. LOPA-based DLW technique combined with optically induced thermal effect (local PEB) shows great advantages over the traditional PEB, such as simple, short fabrication time, high resolution. In particular, it allowed the overcoming of the accumulation effect inherently existed in optical lithography by one-photon absorption process, resulting in small and uniform structures with very short lattice constant.

Two-photon absorption using off-resonant excitation with ultrashort X-ray pulses

SynopsisHigh energy resolution off-resonant X-ray emission spectroscopy (HEROS) was applied to study one-photon (OPA) and two-photon absorption (TPA) processes in metallic copper generated by ultra-short hard X- ray FEL pulses from the Linac Coherent Light Source (LCLS). The OPA and TPA signals were measured using a multiple-crystal von Hamos diffraction spectrometer allowing observation of both the intermediate and final states in the TPA process. The universal scaling of TPA/OPA cross sections is discussed.

Non-resonant below-bandgap two-photon absorption in quantum dot solar cells

We study the optically nonlinear sub-bandgap photocurrent generation facilitated by an extended tailing distribution of states in an InAs/GaAs quantum dots (QDs) solar cell. The tailing states function as both the energy states for low energy photon absorption and the photocarriers extraction pathway. One of the biggest advantages of our method is that it can clearly differentiate the photocurrent due to one-photon absorption (1PA) process and two-photon absorption (2PA) process. Both 1PA and 2PA photocurrent generation efficiency in an InAs/GaAs QD device operated at 1550 nm have been quantitatively evaluated. A two-photon absorption coefficient β = 5.7 cm/GW is extracted.

A superconfiguration approach to multi-electron ionization of Xe under strong x-ray irradiation

The production of highly ionized states in xenon under intense x-ray irradiation, is discussed with the help of specific calculations. The approach, which retains only one-photon absorption processes (photoionization and photoexcitation) as well as Auger and radiative relaxations, makes use of properly defined superconfigurations as a global ensemble of configurations. With a tractable number of (super)levels, we explain the occurrence of the highest charge states observed in experiments.

Calculation of divergent photon absorption in ultrathin films of a topological insulator

We perform linear and nonlinear photon absorption calculations in ultrathin films of a topological insulator on a substrate. Due to the unique band structure of the coupled topological surface states, novel features are observed for suitable photon frequencies, including a divergent edge singularity in the one-photon absorption process and a significant enhancement in the two-photon absorption process. The resonant frequencies can be controlled by tuning the energy difference and coupling the top and bottom surface states. Such unique linear and nonlinear optical properties make ultrathin films of topological insulators promising material building blocks for tunable high-efficiency nanophotonic devices.

Laser-modified one- and two-photon absorption: Expanding the scope of optical nonlinearity

It is shown that conventional one-photon and two-photon absorption processes can be made subject to nonlinear optical control, in each case significantly modifying the efficiency of absorption, through the effect of a secondary, off-resonant stimulus laser beam. The mechanistic origin of these laser-modified absorption processes, in which the stimulus beam emerges unchanged, is traced to higher-order terms in standard perturbation treatments. These normally insignificant terms become unusually prominent when the secondary optical stimulus is moderately intense. Employing a quantum formulation, the effects of the stimulus beam on one-photon and two-photon absorption are analyzed, and calculations are performed to determine the degree of absorption enhancement, and the form of spectral manifestation, under various laser intensities. The implications of differences in selection rules are also considered and exemplified, leading to the identification of dark states that can be populated as a result of laser-modified absorption. Attention is also drawn to the possibility of quantum nondemolition measurements, based on such a form of optical nonlinearity.

UV- and NIR-responsive polymeric nanomedicines for on-demand drug delivery

Ultraviolet (UV) and near infrared (NIR) light-responsive polymeric nanomedicines (e.g., cargo-loaded micelles and vesicles) have increasingly received much attention for their applications in the spatiotemporal and on-demand drug delivery and disease therapy. This UV/NIR-sensitivity is activated via a one-photon and/or two-photon absorption process. The phototriggered micellar disruption and drug release have three mechanisms: (1) the hydrophobicity–hydrophilicity transition, (2) the photocleavage reaction, and (3) the cascade depolymerization reaction (e.g., self-immolative polymers). As NIR light can penetrate deeply into tissues (up to several inches) with less damage and scattering compared with UV and visible light, the polymeric nanomedicines simultaneously exhibiting both UV- and NIR-sensitivity hold great potential in clinical medicine and are especially discussed in this review.