Non-resonant Two-photon Absorption Research Articles

Two-photon chemistry of tetrahydrofuran in clathrate hydrates.

High-lying electronic states hold the potential for new and unusual photochemical reactions. However, for conventional single-photon excitation in the condensed phase, reaching these states is often not possible because the vacuum-ultraviolet (VUV) light required is competitively absorbed by the surrounding matrix rather than the molecule of interest. Here, this hurdle is overcome by leveraging nonresonant two-photon absorption (2PA) at 265 nm to achieve preferential photolysis of tetrahydrofuran (THF) trapped within a clathrate hydrate network at 77 K. Electron spin resonance (ESR) spectroscopy enables direct observation and identification of otherwise short-lived organic radicals stabilized by the clathrate cages, providing clues into the rapid dynamics that immediately follow photoexcitation. 2PA induces extensive fragmentation of enclathrated THF yielding 1-alkyl, acyl, allyl and methyl radicals-a stark departure from the reactive motifs commonly reported in γ-irradiated hydrates. We speculate on the undetected transient dynamics and explore the potential role of trapped electrons generated from water and THF. This demonstration of nonresonant two-photon chemistry presents an alternative approach to targeted condensed phase photochemistry in the VUV energy range.

Theory of two-photon absorption with broadband squeezed vacuum

We present an analytical quantum theoretic model for nonresonant molecular two-photon absorption (TPA) of broadband, spectrally multimode squeezed vacuum, including low-gain (isolated entangled photon pairs) and high-gain (bright squeezed vacuum or BSV) regimes. The results are relevant to the potential use of entangled-light TPA as a spectroscopic and imaging method. We treat the scenario that the exciting light is spatially single mode and is nonresonant with all intermediate molecular states. In the case of high gain, we find that in the case that the linewidth of the final molecular state is much narrower than the bandwidth of the exciting light, bright squeezed vacuum is found to be equally (but no more) effective in driving TPA as is a quasimonochromatic coherent-state (classical) pulse of the same temporal shape, duration, and mean photon number. Therefore, in this case the sought-for advantage of observing TPA at extremely low optical flux is not provided by broadband bright squeezed vacuum. In the opposite case that the final-state linewidth is much broader than the bandwidth of the BSV exciting light, we show that the TPA rate is proportional to the second-order intensity autocorrelation function at zero time delay ${g}^{(2)}(0)$, as expected. We derive and evaluate formulas describing the transition between these two limiting cases, that is, including the regime where the molecular linewidth and optical bandwidth are comparable, as is often the case in experimental studies. We also show that for ${g}^{(2)}(0)$ to reach the idealized form ${g}^{(2)}(0)=3+1/\overline{n}$, with $\overline{n}$ being the mean number of photons per temporal mode, it is required to compensate the dispersion inherent in the nonlinear-optical crystal used to generate the BSV.

Studies on rubidium 5S-5d two-photon absorption

ABSTRACT We studied non-resonant two photon absorption (NRTPA) 5S1/2→5D5/2 of hot Rb atom using a laser emitting at 778nm. The decay channel 5D5/2→6P3/2→5S1/2 is monitored to record the blue fluorescence. Two important aspects of blue fluorescence are explored: (i) photon number statistics under counter-propagating beam geometry, (ii) extraction of a workable discriminator signal by using modulation transfer for offset locking. The blue photon statistics histogram closely follows super–Poissonian distribution revealing the partially coherent or chaotic character under the limit of large photon counts. On the other hand modulation amplitude vs. peak height of 1-st derivative signal reveals that too small or too large modulation is detrimental for extracting discriminator signal. Under weak modulation, the offset stabilized laser attains square root of Allan variance σ(τ) ∼ 1.5 × 10−10 at integration time τ>10s. We propose generation of an offset stabilized chaotic blue light source by coupling (i) and (ii).

Excited States of Thio-2′-deoxyuridine Bearing an Extended π-Conjugated System: 3′,5′-Di-O-acetyl-5-phenylethynyl-4-thio-2′-deoxyuridine

A new thio-2'-deoxyuridine with an extended π-conjugated group was successfully synthesized: 3',5'-di-O-acetyl-5-phenylethynyl-4-thio-2'-deoxyuridine. The thio-2'-deoxyuridine derivative has a large red-shifted absorption band in the UVA region and also shows fluorescence, a rare photo-property among thionucleobases/thionucleosides. The triplet-triplet absorption spectrum and the rate constants (the intrinsic decay rate constant of the triplet state, the self-quenching rate constant, and the quenching rate constant of the triplet state by an oxygen molecule) of the thio-2'-deoxyuridine were obtained by transient absorption spectroscopy. The quantum yield of intersystem crossing and the quantum yield of singlet molecular oxygen formation (ϕΔ) under an oxygen atmosphere were also determined. The ϕΔ value of the new thio-2'-deoxyuridine was found to be substantially higher than all reported values of other thio-2'-deoxyribonucleosides in low oxygen concentrations similar to cancer cell environments. The fluorescence quantum yield depended on the excitation wavelength, revealing certain photochemical reactions in the higher excited singlet states. However, when excited into the higher excited state with non-resonant two-photon absorption, the ϕΔ of the thio-2'-deoxyuridine derivative was found to remain sufficiently large. These findings should be very useful for the development of thio-2'-deoxyribonucleoside-based pharmaceuticals as DNA-specific photosensitizers for photochemotherapy.

Optimal spectral phase control of femtosecond laser-induced up-conversion luminescence in Sm3+:NaYF4 glass

The spectral phase of the femtosecond laser field is an important parameter that affects the upconversion (UC) luminescence efficiency of dopant lanthanide ions. In this work, we report an experimental study on controlling the UC luminescence efficiency in Sm3+:NaYF4 glass by 800-nm femtosecond laser pulse shaping using spectral phase modulation. The optimal phase control strategy efficiently enhances or suppresses the UC luminescence intensity. Based on the laser-power dependence of the UC luminescence intensity and its comparison with the luminescence spectrum under direct 266-nm femtosecond laser irradiation, we propose herein an excitation model combining non-resonant two-photon absorption with resonance-mediated three-photon absorption to explain the experimental observations.

Diffraction and quantum control of wave functions in nonresonant two-photon absorption

In this study, the nonresonant two-photon absorption process in a two-level atom, induced by a weak chirped pulse, is theoretically investigated in the frequency domain. An analytical expression of the wave function expressed by Fresnel functions is obtained, and the two-photon transition probability (TPTP) versus the integral bandwidth, spectral width, and chirp parameter is analyzed. The results indicate that the oscillation evolution of the TPTP result from quantum diffraction of the wave function, which can be explained by analogy with Fresnel diffraction from a wide slit in the spatial domain. Moreover, the ratio between the real and imaginary parts of the excited state wave function and, hence, the atomic polarization, can be controlled by the initial phase of the excitation pulse. In some special initial phase of the excitation pulse, the wave functions with purely real or imaginary parts can be obtained by measuring the population probability. This work provides a novel perspective for understanding the physical details of the interactions between atoms and chirped light pulses in the multiphoton process.

Polarization control of multi-photon absorption under intermediate femtosecond laser field**Project supported by the Program of Introducing Talents of Discipline to Universities (Grant No. B12024), the National Natural Science Foundation of China (Grant Nos. 51132004, 11474096, 11547216, 11547220, and 11604199), the Science Fund from the Science and Technology Commission of Shanghai Municipality (Grant No. 14JC1401500), and the Higher Education Key Program

It has been shown that the femtosecond laser polarization modulation is a very simple and well-established method to control the multi-photon absorption process by the light–matter interaction. Previous studies mainly focused on the multi-photon absorption control in the weak field. In this paper, we further explore the polarization control behavior of multi-photon absorption process in the intermediate femtosecond laser field. In the weak femtosecond laser field, the second-order perturbation theory can well describe the non-resonant two-photon absorption process. However, the higher order nonlinear effect (e.g., four-photon absorption) can occur in the intermediate femtosecond laser field, and thus it is necessary to establish new theoretical model to describe the multi-photon absorption process, which includes the two-photon and four-photon transitions. Here, we construct a fourth-order perturbation theory to study the polarization control behavior of this multi-photon absorption under the intermediate femtosecond laser field excitation, and our theoretical results show that the two-photon and four-photon excitation pathways can induce a coherent interference, while the coherent interference is constructive or destructive that depends on the femtosecond laser center frequency. Moreover, the two-photon and four-photon transitions have the different polarization control efficiency, and the four-photon absorption can obtain the higher polarization control efficiency. Thus, the polarization control efficiency of the whole excitation process can be increased or decreased by properly designing the femtosecond laser field intensity and laser center frequency. These studies can provide a clear physical picture for understanding and controlling the multi-photon absorption process in the intermediate femtosecond laser field, and also can provide a theoretical guidance for the future experimental realization.

Protecting and accelerating adiabatic passage with time-delayed pulse sequences.

Using numerical simulations of two-photon electronic absorption with femtosecond pulses in Na2 we show that: (i) it is possible to avoid the characteristic saturation or dumped Rabi oscillations in the yield of absorption by time-delaying the laser pulses; (ii) it is possible to accelerate the onset of adiabatic passage by using the vibrational coherence starting in a wave packet; and (iii) it is possible to prepare the initial wave packet in order to achieve full state-selective transitions with broadband pulses. The findings can be used, for instance, to achieve ultrafast adiabatic passage by light-induced potentials and understand its intrinsic robustness.

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.

Observation and symmetry-based coherent control of transient two-photon absorption: the bright side of dark pulses.

We present and experimentally demonstrate for the first time the observation and femtosecond coherent control over the temporal evolution of a transient population that is excited via nonresonant two-photon absorption. Based on symmetry properties of the two-photon absorption process, the exciting femtosecond pulses are phase-shaped to photoinduce different evolutions of the transient excited population for a given final excited population. As a study case, we focus here on the attractive case of two-photon dark pulses that, although inducing zero final population (hence, the terminology of "dark pulses"), they induce a transient excited population during the pulse irradiation that can significantly deviate from zero. This nonzero transient population can be viewed as the bright side of such dark pulses. The symmetry-based coherent control is demonstrated first with dark pulses that we shape to induce transient excited population that at all times is kept below different target levels. Then, it is further demonstrated with pairs of dark pulses where one is rationally shaped to induce temporal evolution of the transient excited population that is the inverse of the evolution induced by the other. The work is conducted in the weak-field regime with the sodium atom as the model system. The approach developed here is general, conceptually simple, and very effective.

Quantum focusing and coherent control of nonresonant two-photon absorption in frequency domain.

We theoretically investigate the nonresonant two-photon absorption (TPA) process in a two-level atom induced by a weak chirped pulse in the frequency domain. According to the extremum condition of the two-photon transition probability (TPTP) at the transition center frequency, we propose a Fresnel-inspired pulse tailoring scheme for TPA that is significantly different from that of Broers etal. [Phys. Rev. A46, 2749 (1992)]. Using this scheme, the TPTP can be focused or eliminated completely by constructively or destructively modulating various pathways of the quantum interference. Our results are a significant improvement on those obtained by Broers etal. and will have potential applications in selective two-photon microscopy and spectroscopy.

Collision induced modification of spectral lines in the first autoionization region of barium

The spectrum of barium above the first ionization potential is significantly modified by collisions with rare gas atoms. Atomic Ba vapor was produced in a heat-pipe oven. The two ground state electrons of Ba were excited simultaneously using non-resonant two-photon absorption to populate the 5d 3/2 n d 3/2, J = 0, 2 autoionizing states. The spectral region corresponding to this series was studied when Ba atoms were unperturbed, and when they were perturbed by the noble gases Ar, Kr, and Xe. Besides the expected shift and broadening of autoionizing series due to collisions with rare gases, we observed new spectral bands and significant changes to the shape of the existing lines.

Steering the optimization pathway in the control landscape using constraints

We show how additional constraints, restricting the spectrum of the optimized pulse or confining the system dynamics, can be used to steer optimization in quantum control towards distinct solutions. Our examples are multi-photon excitation in atoms and vibrational population transfer in molecules. We show that a spectral constraint is most effective in enforcing non-resonant two-photon absorption pathways in atoms and avoiding unnecessarily broad spectra in Raman transitions in molecules. While a constraint restricting the system to stay in an allowed subspace is also capable of identifying non-resonant excitation pathways, it does not avoid spurious peaks in the pulse spectrum. Both constraints are compatible with monotonic convergence but imply different additional numerical costs.

Optimal control under spectral constraints: enforcing multi-photon absorption pathways

Shaped pulses obtained by optimal control theory often possess unphysically broad spectra. In principle, the spectral width of a pulse can be restricted by an additional constraint in the optimization functional. However, it has so far been impossible to impose spectral constraints while strictly guaranteeing monotonic convergence. Here, we show that Krotov’s method allows for simultaneously imposing temporal and spectral constraints without perturbing monotonic convergence, provided the constraints can be expressed as positive semi-definite quadratic forms. The optimized field is given by an integral equation which can be solved efficiently using the method of degenerate kernels. We demonstrate that Gaussian filters suppress undesired frequency components in the control of non-resonant two-photon absorption.

Non-poissonian formation of multiple excitons in photoexcited CdTe colloidal quantum qots by femtosecond nonresonant two-photon absorption

Using direct multiexcitonic spectroscopy, we experimentally observe for the first time the non-Poissonian formation of multiple excitons by femtosecond nonresonant two-photon absorption process in semiconductor colloidal quantum dots (QDs). Each of the multiple excitons is individually generated via the absorption of a pair of photons during the femtosecond pulse irradiation. The non-Poissonian distribution of the generated excitons is reflected as a non-quadratic dependence on the pulse intensity of the average number of excitons per QD. This is the main observation of the present work. It is explained by a multiexcitonic formation model that is based on the phenomenon of intrapulse state filling of the few quantum electronic states accessed by the two-photon transitions. The experiments are conducted with 3.9-nm CdTe QDs in room-temperature hexane solution using the femtosecond pump-probe transient absorption technique, where an intense pump pulse generates the excitons and a weak probe pulse measures their number via intraband one-photon absorption.

NON-RESONANT TWO-PHOTON ABSORPTION CONTROL BY TWO TIME-DELAYED LASER PULSES

In this paper, we theoretically investigate the control of the non-resonant two-photon absorption induced by two time-delayed laser pulses, and an analytical solution for the dependence of the two-photon transition probability on the time delay and relative carrier-envelope phase of the two laser pulses is achieved. We show that the two-photon absorption can be significantly enhanced or completely suppressed by varying the time delay between the two laser pulses or their relative carrier-envelope phase. We also show that the two-photon absorption can be selectively excited when two excited states are simultaneously excited. Furthermore, we discuss the two-photon absorption control in the molecular system and analyze the effect of the absorption bandwidth on the control efficiency of the two-photon absorption.

“Dark” Excited States of Diphenylacetylene Studied by Nonresonant Two-Photon Excitation Optical-Probing Photoacoustic Spectroscopy

Optical probing photoacoustic spectroscopy (OPPAS), a photothermal calorimetric technique, was applied to investigate one-photon forbidden “dark” electronically excited singlet states of diphenylacetylene (DPA), belonging to the D2h point group. When 502 nm light from a pulsed OPO laser was focused into a DPA hexane solution, an acoustic wave was detected as a transient angular deflection of the probe beam (He–Ne laser). The laser power dependence of the OPPAS signal was estimated to be 1.9 ± 0.2, suggesting two-photon absorption for acoustic generation. With the OPPAS technique, we successfully obtained a nonresonant two-photon absorption spectrum of DPA in solution for the first time. The two-photon allowed 11B3g and 21Ag states were found to be above the one-photon allowed 11B1u state. These results show that OPPAS is a highly sensitive technique applicable to two-photon absorption spectral measurements of nonfluorescent species.

Saturated two-photon absorption of single-frequency radiation in gaseous media

A saturated nonresonant two-photon absorption (TPA) theory of quasi-monochromatic radiation by an atom is developed in a model of a three-level cascade quantum system. It is shown that doubled-frequency radiation, arising from a multipole interaction of radiation with the dipole-forbidden transition, experiences spatial oscillations at arbitrary intensities of the pump. The influence of the total phase of the waves with the initial and doubled frequencies on TPA is considered under conditions of ring frequency mixing in a medium.

Highly selective population of two excited states in nonresonant two-photon absorption

A nonresonant two-photon absorption process can be manipulated by tailoring the ultra-short laser pulse. In this paper, we theoretically demonstrate a highly selective population of two excited states in the nonresonant two-photon absorption process by rationally designing a spectral phase distribution. Our results show that one excited state is maximally populated while the other state population is widely tunable from zero to the maximum value. We believe that the theoretical results may play an important role in the selective population of a more complex nonlinear process comprising nonresonant two-photon absorption, such as resonance-mediated (2+1)-three-photon absorption and (2+1)-resonant multiphoton ionization.

Loading rate of Yb+ loaded through photoionization in radiofrequency ion trap

We investigate the loading rate of Yb+ ions loaded through photoionization in a radiofrequency trap. The absolute or relative number of the loaded trapped ions is measured by use of an electric resonance of the secular motion. This method is applicable even in the presence of anharmonicity. In two-color photoionization, where the first-excitation laser drives the 1S0–1P1 transition in the Yb atom and the second one ionizes the atom from the 1P1 state, the loading rate is at its highest by the excitation of the ionization potential. A similar loading rate is observed at the second-laser wavelength around 369.5 nm, which is the wavelength for the cooling transition of Yb+. We estimate the loading cross section to be 40(15) Mb for the two-color excitation of the ionization potential. The excitation of the Yb atoms in the Rydberg states is detected by the enhancement of the loading rate. By irradiation with only the first-excitation laser, Yb+ is produced at a rate three orders of magnitude smaller than that when the non-resonant two-photon absorption from the 1P1 state is the dominant process. We also measure the charge-exchange rate between Yb+ and Yb, and discuss its effect on isotope-selective photoionization loading.