The two-photon excitation spectrum of triphenylene in n-heptane single crystals

A comparison of the one-and two-photon absorption spectra of triphenylene in n-heptane single crystals at 1.6. K reveals that the lowest singlet state (S₁) is of ¹A′₁ symmetry while the second singlet state(S₂) has ¹A′₂ symmetry, in contradiction with the commonly accepted assignment.     

Measurement of kinetic processes in photoexcited stilbene solutions

The kinetics of photophysical processes has been measured in stilbene solutions in the temperature range between ?40°C and 20°C. The population of the S₁ level excited by two-photon absorption (TPA) and of secondary populated levels has been investigated using a probe beam method. It was found an energy barrier ΔE = 5 × 10² cm^?1 of the thermically activated transition S₁ → 1′. The rate parameter of this transition is determined to be k^?1_11′, ≈ 2 ps at very high temperatures.     

Laser excited S2 → S1 and S1 → S0 emission spectra and the S2 → Sn absorption spectrum of azulene in solution

We present the S₁ → S₀ fluorescence spectrum, between 740 and 940 nm, of azulene solutions (10^?3 M in methanol) excited with a Q-switched ruby laser. The nitrogen-laser excited S₂ → S₁ fluorescence spectrum, between 700 and 930 nm, is also reported. The transient S₁ → S_n spectrum between 500 and 650 nm was studied, using synchronous nitrogen laser and dye laser excitation. The S₅ (¹B₁(3)) state of azulene was found to be located at 45500 cm^?1 and the cross section σ₂₅ of the transient absorption S₂ → S₅ is estimated to be 3 × 10^?18 cm²/molecule.     

Picosecond spectroscopic measurement of very fast intersystem crossing for 9,10-dioxa-anti-bimanes

Picosecond spectroscopy, following the buildup of T₁ → T_n absorption (maximum at 420 nm), shows that the T₁ state of 1,5-diazabicyclo[3,3,0]octa-3,7-diene-2,6-diones(9,10-dioxa-anti-bimanes) is formed within about 10 ps. The nature of the T₁ state was confirmed by decay rates of T₁ → T_n absorption in acetonitrile (n = 0.375 cP, k_nr = 4.5 × 10⁵ s^?1), 1,2-ethanediol (n = 26 cP, k_nr = 1.5 × 10⁴ s^?1 and glycerol (n = 1400 cP, k_nr = 1.3 × 10³ s^?1). The very fast intersystem crossing is ascribed to the proximity of a ³nπ* state to the ππ* (S₁ state produced by light absorption (El-Sayed rule).     

Nonlinear optical properties of systems based on (tetra-15-crown-5-phthalocyaninato)indium(III)

The nonlinear optical properties of solutions of (2,3,9,10,16,17,23,24-tetra-15-crown-5-phthalocyaninato)indium(III) [(15C5)₄Pc]In(OH) in tetrachloroethane (TCE) have been studied by the z-scan method. It has been found that a nonlinear optical response is due to supramolecular associates formed in a tetrachloroethane solution by heating to 90°C/slow cooling to room temperature cycling. The formation of the supramolecular associates has been studied by atomic force microscopy (AFM) and electronic absorption spectroscopy (EAS). It has been shown that a single thermal treatment of [(15C5)₄Pc]In(OH) solutions in TCE results in the predominant formation of dimers, as evidenced by both a short-wavelength shift of the Q-absorption band of the monomeric complex (λ_max = 692 nm) to the band of λ_max = 653 nm and height doubling of molecular entities as measured by AFM. The dimers are responsible for the two-photon absorption measured in the femtosecond range, which has a relatively high cross section of σ₂ = 1.38 × 10^?46 cm⁴ s/(molecule, photon) or 1.38 × 10⁴ GM. According to the AFM data, three cycles of heat treatment of the solution leads to the formation of supramolecular assemblies of about 200 nm length. The optical spectrum exhibits long-wavelength absorption at λ_max = 841 nm and the long-wavelength edge near 1300 nm. In the case of nanosecond 1064-nm laser irradiation, the linear absorption S ₀ → S ₁ is primary, having the cross section of σ₀ = α₀/N = 2.3 × 10^?20 cm². The known high quantum yield (close to unity) of triplet states of indium phthalocyanines suggests that the main nonlinear optical effect is determined by intersystem crossing S ₁ → T ₁ and triplet-triplet absorption T ₁ → T ₂. The absorption cross section is σ _T-T = 1.14 × 10^?19 cm².     

Spectroscopy and dynamics of 9,10-dichloroanthracene-Arn van der Waals complexes

In this paper we report on the measurements of the absorption spectra of large van der Waals complexes in planar supersonic jets. The absorption spectra and the fluorescence excitation spectra of the complexes of 9,10-dichloroanthracene (DCA) with Ar atoms are reported for the S₀ → S₁(0) vibrationless transition of DCA·Ar_n (n = 1?6), and from the S₀ → S₁ (1390 cm^?1) transition of DCA·Ar_n (n = 1?4). Information on the structure of these complexes was inferred from the additivity of the spectral shifts per added rare-gas atom (ASSRA) for DCA·AR_n (n = 1.2) and from deviations from the ASSRA for CDA-Ar_n (n = 3?6). The vibrational predissociation (VP) dynamics of DCA-Ar_n (n = 1?3) complexes was interrogated by fluorescence quantum yield, Y, measurements. The value of the S₁ (1390 cm^?1) state of DCA·Ar_n (n = 1?3) exhibits a dramatic enhancement relative to that of DCA. Utilizing the dependence of Y on the excess vibrational energy of bare DCA, we were able to estimate the internal energy of the fragments resulting from VP of DCA·Ar_n of DCA·Ar_n (n = 1?3). An upper limit of ? 100 ps was estimated for the VP (and/or vibrational energy redistribution) lifetime from the S₁ (1390 cm^?1) state of DCA·Ar₃.     

The polarised two-photon excitation spectrum of benzene monocrystals at 6 eV

The two-photon excitation spectrum of a benzene single crystal at 4.2 K has been recorded in the region of the second absorption system. The onset of two-photon absorption occurs near 46 500 cm^?1 (quoted as a two-photon frequency). The spectrum has the appearance of a forbidden transition in that the system begins with weak lines which become dominated by an intense continuum at higher energies. The two-photon cross section at 55 000 cm^?1 (the limit reached in this study) is about 200 times greater than at 47 490 cm^?1 although the peak of this strongly allowed system has not yet been reached. The fwhm of the bands near 47 000 cm^?1 is 280 cm^?1, the same as in the one-photon spectrum at these energies. The polarisation ratio is much the same over the entire energy range, and is consistent with the two-photon operators (xz, yz) or (zz). An analysis of all the data available from the one- and two-photon spectra suggests that the transition is ¹B_1u ← ¹A_1g in which the vibronic intensity is derived from the ¹E_1u state in the one-photon and ¹E_1g in the two-photon spectrum.     

Interpretation of the optical dephasing time and lineshape function in the S0 → T1 exciton transitions of 1,4-dibromonaphthalene

The lineshape function for the S₀ → T₁ absorption in 1,4-dibromonaphthalene (DBN) is analyzed in terms of exchange theory. It is shown that the dominant optical dephasing mechanism for the electric dipole transition to the k = 0 state in the band results from the absorption and emission of a low energy optic phonon. This process dephases the optical absorption because of frequency differences of the phonon in the ground and excited state. In addition, it is shown how to extract the energy of the phonon responsible for dephasing, the phonon absorption rate, and the lifetime in the phonon promoted state from the data. The analysis of the data for DBN shows that very little dephasing of the optical transition occurs before ≈ 15 K but from 15 K to ≈ 40 K the singlet-triplet transitions to site I (20192 cm^?1) and site II (20245 cm^?1) are dephased by absorption and emission of an ≈ 38 cm^?1 and 45 cm^?1 phonon respectively. The phonon absorption rates by the k = 0 state in the exciton band are similar for both sites being 5 × 10⁶ s^?1 and 3 × 10⁵ s^?1 at 4 K and 7 × 10¹¹ s^?1 and 4 × 10¹¹ s^?1 at 30 K for site I and II respectively. Finally, the lifetimes in the phonon promoted state for sites I and II are 0.23 and 0.28 ps over the range 15–40 K.     

Population hole-burning using a triplet reservoir: S1 ← S0 transition of zinc porphin in n-octane

Optical hole-burning has been observed in the S₁ ← S₀ absorption of zinc porphin in n-octane by selective depletion of the ground state population and storage in the mestastable triplet state. In this way the homogeneous linewidths of S₁ ← S₀ for molecules in A and B sites of n-octane were measured between 1.6 and 4.5 K. Thermally induced dephasing was observed for B-site molecules with an activation energy of 14 cm^?, equal to the separation between the two electronic components of S₁.     

The two-photon spectrum of toluene vapor

The two-photon excitation spectrum of toluene-h₈ and toluene-d₈ vapor has been recorded under low resolution (1 cm^?1) in the region of the S₁ ← S₀ (¹B₂ ← ¹A₁) transition. Although the electronic transition is formally allowed in two-photon spectroscopy, a large fraction of intensity exists in a subsystem induced by the out-of-phase CC stretching vibration ν₁₄ (b₂). Band contours associated with each of the two assigned tensor components of the transition are identified and partially analyzed by comparison with the two-photon contours of fluorobenzene.     

Ultraviolet emission of molecular chlorine

The UV emission of Cl₂ from a new valence-shell state having 0⁺_u symmetry (T_c ≈ 59774 cm^?1, r_c ≈ 3.0 Å) was observed by focusing ≈ 500 nm laser radiation to gaseous chlorine. Excitation was achieved by virtual two-photon absorption from the B ³Π_0⁺u state formed by single-photon absorption stepwisely. The emission spectra showed transitions to the ground state as well as to the repulsive grade estate dissociating to Cl²P) + Cl(²P) products.     

Absorption and emission spectra of the lowest triplet state in hexachloroacetone

T₁ ← S₀ absorption and T₁ → S₀ phosphorescence spectra of neat cystalline hexachloroacetone have been analyzed at 4.2°K. From the lifetime and energy the upper state is assigned as ³nπ^*. The spectra are sharp compared to other aliphatic ketones, with the 0-0 band at 26 248 ± 2 cm ^?1. The phosphorescence shows two strong progressions; one involving the CO stretching mode at 1784 cm^?1 (x), the other a long progression of at least 8 bands involving a mode at 143 cm^t-1 (a). The 143 cm^?1 progression forming mode can best be asigned to the CO out-of-plane wagging vibration. The absorption shows the same two strong progressions, reduced in frequency to 1270 cm^t-1 and 123 cm^?1, respectively, but with the progression in mode a broadened with increasing n. The broadening is interpreted as arising from inversion doublets; the close harmonicity up to n = 5 allowing the potential barrier to inversion to be estimated as > 700 cm^?1. A feature of the spectra is the absence of low frequency torsional modes suggesting lack of pseudo Jahn-Teller distortion of the triplet state potential surface. For comparison, the phosphorescence of crystalline hexafluoroacetone was also studied at 4.2°K. The spectrum exhibits broad bandedness with a 00 band tentatively assigned at 26 870 ± 20 cm^?1.     

Electronic energy transfer from the S2 state of rhodamine 6G

In this paper we present the results of an experimental study of intermolecular electronic energy transfer (EET) from the short-lived Second excited singlet state of rhodamine 6G (R6G) to the ground state of 2,5-bis [5′-tert-butyl-2-benzoxazolyl] thiophene (BBOT). The S₂ state of the donor was excited by sequential, time-delayed, two-photon excitation (STDTPE) utilizing the second harmonic and the first harmonic of a mode-locked Nd³⁺: glass laser, while the EET process was interrogated by monitoring the enhancement of the S₁ → S₀ fluorescence of BBOT. The enhancement of the fluorescence intensity of BBOT was found to be linear in the energies of the two exciting pulses, and linear in the concentration of the energy acceptor (over the BBOT concentration range of (0.3–7) × 10^?5 M), which is in accord with the predictions of the Forster—Dexter mechanism for resonant EET from an ultrashort-lived donor state at low acceptor concentrations. Quantitative measurements of the S₂ → S₀ fluorescence yield in R6G solution directly excited by STDTPE and of the S₁ → S₀ fluorescence of BBOT from R6G + BBOT solutions resulting from EET led to the values of Y_D(S₂ → S₀) = (2.1 ± 0.5) × 10^?6 for the emission quantum yield of the S₂ state of R6G and τr_D(S₂) ≈ 3 × 10^?14 s for the lifetime of the metastable S₂ state of this molecule.     

Effect of rotational relaxation on the intensity and polarization of fluorescence emission caused by sequential two-photo excitation

General formulas are derived for the intensity and the degree of polarization of the S_m-fluorescence emission (m ? 2) of a sample excited by the sequential two-photon excitation process (S_n ← S₁ ← S₀, n ? 2) with plane-polarized pulsed light. They show how the S_m-fluorescence intensity and anisotropy depend on the relative orientation of the relevant transition dipoles within a molecule and on the degree of rotational relaxation of molecules in the intermediate state (S₁) and in the S_m state (for the case m = n), or in the S_n → S_m process (m ≠ n).     

Theoretical study on geometry and spectroscopic properties of 1,1′-binaphthyl in the electronic ground and first excited singlet states

Equilibrium geometries for the electronic ground and first excited singlet states of 1,1'-binaphthyl have been calculated by minimization of the total energy with respect to all internal coordinates. Using these results, an interpretation of the fluorescence S₁→ S₀ and absorption spectra S_m ← S₀ and S_n ← S₁ in rigid and fluid solutions is given.For the first time the equilibrium geometry of the first excited singlet state of 1, 1′-binaphthyl has been calculated. On excitation to the S₁ state the dihedral angle θ between the two naphthalene moieties is de- creased from 61 ° to 41 °. A detailed survey of CH bond lengths in the S₀ and S₁ states has been given. This result should be of particular importance for the theoretical treatment of radiationless transitions.Using equilibrium geometries for the S₀ and S₁ states a satisfactory interpretation of the S_m ← S₀ and S_n ← S₁ absorption spectra as well as of the fluorescence spectra in fluid and rigid solutions can be given. Concerning the S_n ← S₁ absorption spectrum in fluid solution, the calculations predict a strong absorption (A ← B transition) in the still uninvestigated region of energies lower than 11000 cm^?1.From the results of this paper and of other calculations it can be concluded that the Warshel-Karplus method yields reliable equilibrium geometries for electronic ground and excited states of unsaturated hydrocarbons [22,23].     

Two-Photon Absorption and Excited-State Refractions in Anthraquinone Dyes

We examine the nonlinear optical properties of solutions of 9,10-anthraquinone, 1,4-dihydroxy-anthraquinone, 5,8-dichloro-1,4-dihydroxy-anthraquinone and 1,4-bisethylamino-anthraquinone by means of the intensity-dependent transmission and the Z-scan method with 532 nm 8 ns pulses. The results demonstrated that the 9,10-anthraquinone displayed a two-photon absorption (TPA) character. The molecular TPA cross section of this compound is estimated as σ₂ = 7.22 × 10^?19 cm⁴/GW or σ₂ = 26.96 × 10^?48 cm⁴/photon/s, respectively, and an essential state of ‘m¹Ag’, which should be located near the 2ω virtual transition state, is predicted. On the other hand, the effective excited-state nonlinear refractive coefficients n₂^eff of these anthraquinones are found to be ～10^?10 esu, which are comparable with those highly conjugated planar molecules of tetrabenzporphyrins and phthalocyanines.     

The fluorescence of all-trans diphenyl polyenes

The temperature dependence of the fluorescence and fluorescence excitation spectra of all-trans diphenyl hexathene (DPH) and octatetraene (DPO) in six solvents confirms the S₁(¹A_g*) and S₂(¹B_u*) state assignment, and determines their energy difference ΔE. The S₁ fluorescence rate parameter k_F depends on ΔE, the solvent refractive index n, the S₂ (n = 1) fluorescence rate parameter k_F20 (2.23 × 10⁸ s^?1 for DPH, 2.33 × 10⁸ s^?1 for DPO), and the S₂-S₁ coupling matrix element V (745 cm^?1 for DPH, 500 cm^?1 for DPO). The S₁ fluorescence is induced by ¹B_u*-¹A_g* potential interaction (PI), via a b_u vibrational mode (≈ 900 cm^?1), and not by vibronic coupling. The main S₁ radiationless transition, rate parameter k_R, is thermally-activated internal rotation through an angle θ about the central ethylenic bond(s). The PI distorts the S₁ (θ) potential surface and thus influences k_R.     

Nonlinear optical properties of polyvinylcarbazole composites with graphene

The study has focused on polyvinylcarbazole (PVK) composites with graphene. It has been shown that there is a noticeable nonadditive shoulder on the long-wavelength edge of the optical absorption of PVK in these samples, which can be attributed to the formation of a charge-transfer complex between PVK as a donor and graphene as an acceptor. The formation of the complex causes a significant nonlinear optical effect in the PVK/graphene composite. The revealed increase in both the nonlinearity coefficient with increasing laser intensity and the cross section with increasing incident energy density is due to the formation of the graphene^?· radical anion, an additional species contributing to nonlinear absorption, with an increase in the radiation energy density. Nonlinear optical properties of PVK composites with graphene isolated from a solution in tetrachloroethane after 1.5-h centrifugation (sample 1) have been considered. It has been suggested that a significant decrease in optical transmission of laser radiation by the composite T _OA = 0.4 at an energy density at focus of 502 J/cm² is due to the formation of the PVK/graphene charge-transfer complex responsible for the nonadditive shoulder on the long-wavelength optical absorption edge of PVK. During photoexcitation of graphene in the PVK/graphene composites at a laser wavelength of 1064 nm, mobile holes are generated in PVK, indicating the formation of graphene^?· radical anions as a result of charge transfer from PVK to photoexcited graphene. The observed increase in both β with an increase in the laser radiation intensity and the cross section (σ_exc — σ₀) with an increase in the incident energy density may be due to either the contribution of nonlinear transitions (S ₀ → S ₂, S ₀ → S ₁ → S ₂, T ₁ → T ₂) or the formation of the additional species, the graphene-· radical anions, participating in nonlinear absorption by increasing the energy density at the focus (F _foc, J/cm²).     

Photoelectron spectroscopy of transition metal-sulfur cluster anions

Metal (M)-sulfur cluster anions (M = Ag, Fe and Mn) have been studied using photoelectron spectroscopy (PES) with a magnetic-bottle type time-of-flight electron spectrometer. The M_nS _m ^? cluster anions were formed in a laser vaporization cluster source. For Ag-S, the largest coordination number of Ag atoms (n _max) is generally expressed as n _max =2m ? 1 in each series of the number of S atoms (m). For Fe?S and Mn?S, it was found that the stable cluster ions are the ones with compositions of n=m and n=m±1. Their electron affinities were measured from the onset of the PES spectrum. For Ag?S, the EAs of Ag₁S_m are small and around 1 eV, whereas those of Ag_nS_m (_n ≥ 2) become large above 2 eV. The features in the mass distribution and PES suggest that Ag₂S unit is preferentially formed with increasing the number of Ag atoms. For Fe?S and Mn?S, the PES spectra of Fe_nS _m ^? /Mn_nS _m ^? show a unique similarity at n ≥ m, indicating that the Fe/Mn atom addition to Fe_nS _n ^? /Mn_nS _n ^? has little effect on the electronic property of Fe_nS_n/Mn_nS_n. The PES spectra imply that the Fe_nS_n cluster is the structural framework of these clusters, as similarly as the determined structure of the Fe_nS_n cluster in nitrogenase enzyme.     

Energy levels of iodine monochloride near the first dissociation limit

Absorption transitions to vibrational levels close to the A state dissociation limit of ICI have been examined using a two-photon sequential absorption technique. The discrete rotational structures of I³⁷ Cl bands to within 0.7 cm^?1 of the limit have been selectively excited and analysed. A value of 17557.514 ± 0.030 cm^?1 has been obtained for the I(²P^o_{$\text{3}\text{2}$}) + Cl(²P^o_{$\text{3}\text{2}$}) dissociation energy D_e, relative to the minimum of the ICI ground state potential well. The two-photon technique can be used to excite and display separately the high resolution absorption spectra of different isotopic species of a molecule which are contained in a mixture.