Direct observation of a sulfonyl azide excited state and its decay processes by ultrafast time-resolved IR spectroscopy

The photochemistry of 2-naphthylsulfonyl azide (2-NpSO(2)N(3)) was studied by femtosecond time-resolved infrared (TR-IR) spectroscopy and with quantum chemical calculations. Photolysis of 2-NpSO(2)N(3) with 330 nm light promotes 2-NpSO(2)N(3) to its S(1) state. The S(1) excited state has a prominent azide vibrational band. This is the first direct observation of the S(1) state of a sulfonyl azide, and this vibrational feature allows a mechanistic study of its decay processes. The S(1) state decays to produce the singlet nitrene. Evidence for the formation of the pseudo-Curtius rearrangement product (2-NpNSO(2)) was inconclusive. The singlet sulfonylnitrene (1)(2-NpSO(2)N) is a short-lived species (τ ≈ 700 ± 300 ps in CCl(4)) that decays to the lower-energy and longer-lived triplet nitrene (3)(2-NpSO(2)N). Internal conversion of the S(1) excited state to the ground state S(0) is an efficient deactivation process. Intersystem crossing of the S(1) excited state to the azide triplet state contributes only modestly to deactivation of the S(1) state of 2-NpSO(2)N(3).     

Early events in the photochemistry of aryl azides from femtosecond UV/Vis spectroscopy and quantum chemical calculations

The photochemistry of para- and ortho-biphenylyl azides and 1-naphthyl azide was studied by ultrafast spectroscopy. In every case, the singlet azide second excited states were observed by transient absorption spectroscopy and were found to have lifetimes of hundreds of femtoseconds. The decay of the S(2) states of the azides was accompanied by the growth of transient absorption of the corresponding singlet nitrenes. The intermediate S(1) state of the azides could not be observed due to its low instantaneous concentration resulting from fast fragmentation and nitrene formation. Quantum chemical calculations predict that the S(2) state of the azide is bound and that there is a much lower barrier toward arylnitrene formation from the S(1) state of the azide. Vibrational cooling of para-biphenylnitrene (11 ps) was experimentally observed. The lifetime of singlet ortho-biphenylnitrene was 16 ps in acetonitrile and was not affected by perdeuteration of the aryl ring. The lifetime of singlet 1-naphthylnitrene is 12 ps in acetonitrile at ambient temperature.     

Early events in the photochemistry of 2-naphthyl azide from femtosecond UV/Vis spectroscopy and quantum chemical calculations: direct observation of a very short-lived singlet nitrene

Exposure of 2-naphthyl azide in acetonitrile at ambient temperature to femtosecond pulses of 266 nm light produces a transient absorption with maxima at 350 and 420 nm. The carrier of the 350 nm band decays more rapidly than that of the 420 nm band which has a lifetime of 1.8 ps. Analogous experiments with 1-chloro-2-naphthyl azide in methanol allow the assignment of the 350 nm band to a singlet excited state of 2-naphthyl azide and the carrier of the 420 nm band to singlet 2-naphthylnitrene. This reactive intermediate has the shortest lifetime of any singlet nitrene observed to date and is a true reactive intermediate. Computational studies at the RI-CC2 level of theory support these conclusions and suggest that initial excitation populates the S2 state of 2-naphthyl azide. The S2 state, best characterized as a pi --> (pi*, aryl) transition, has a geometry similar to S0. S2 of 2-naphthyl azide can then populate the S1 state, a pi --> (in-plane, pi*, azide) excitation, and in the S1 state, electron density is depleted along the proximal N-N bond. S1 is dissociative along that N-N coordinate to form the singlet nitrene, and with a barrier of only approximately 5 kcal/mol for N2 extrusion.     

Ultrafast spectroscopy and computational study of the photochemistry of diphenylphosphoryl azide: direct spectroscopic observation of a singlet phosphorylnitrene

The photochemistry of diphenylphosphoryl azide was studied by femtosecond transient absorption spectroscopy, by chemical analysis of light-induced reaction products, and by RI-CC2/TZVP and TD-B3LYP/TZVP computational methods. Theoretical methods predicted two possible mechanisms for singlet diphenylphosphorylnitrene formation from the photoexcited phosphoryl azide. (i) Energy transfer from the (π,π*) singlet excited state, localized on a phenyl ring, to the azide moiety, thereby leading to the formation of the singlet excited azide, which subsequently loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. (ii) Direct irradiation of the azide moiety to form an excited singlet state of the azide, which in turn loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. Two transient species were observed upon ultrafast photolysis (260 nm) of diphenylphosphoryl azide. The first transient absorption, centered at 430 nm (lifetime (τ) ～ 28 ps), was assigned to a (π,π*) singlet S(1) excited state localized on a phenyl ring, and the second transient observed at 525 nm (τ ～ 480 ps) was assigned to singlet diphenylphosphorylnitrene. Experimental and computational results obtained from the study of diphenyl phosphoramidate, along with the results obtained with diphenylphosphoryl azide, supported the mechanism of energy transfer from the singlet excited phenyl ring to the azide moiety, followed by nitrogen extrusion to form the singlet phosphorylnitrene. Ultrafast time-resolved studies performed on diphenylphosphoryl azide with the singlet nitrene quencher, tris(trimethylsilyl)silane, confirmed the spectroscopic assignment of singlet diphenylphosphorylnitrene to the 525 nm absorption band.     

Time-resolved resonance Raman and computational investigation of the influence of 4-acetamido and 4-N-methylacetamido substituents on the chemistry of phenylnitrene

A time-resolved resonance Raman (TR(3)) and computational investigation of the photochemistry of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide in acetonitrile is presented. Photolysis of 4-acetamidophenyl azide appears to initially produce singlet 4-acetamidophenylnitrene which undergoes fast intersystem crossing (ISC) to form triplet 4-acetamidophenylnitrene. The latter species formally produces 4,4'-bisacetamidoazobenzene. RI-CC2/TZVP and TD-B3LYP/TZVP calculations predict the formation of the singlet nitrene from the photogenerated S(1) surface of the azide excited state. The triplet 4-acetamidophenylnitrene and 4,4'-bisacetamidoazobenzene species are both clearly observed on the nanosecond to microsecond time-scale in TR(3) experiments. In contrast, only one species can be observed in analogous TR(3) experiments after photolysis of 4-N-methylacetamidophenyl azide in acetonitrile, and this species is tentatively assigned to the compound resulting from dimerization of a 1,2-didehydroazepine. The different photochemical reaction outcomes for the photolysis of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide molecules indicate that the 4-acetamido group has a substantial influence on the ISC rate of the corresponding substituted singlet phenylnitrene, but the 4-N-methylacetamido group does not. CASSCF analyses predict that both singlet nitrenes have open-shell electronic configurations and concluded that the dissimilarity in the photochemistry is probably due to differential geometrical distortions between the states. We briefly discuss the probable implications of this intriguing substitution effect on the photochemistry of phenyl azides and the chemistry of the related nitrenes.     

Ultrafast infrared and UV-vis studies of the photochemistry of methoxycarbonylphenyl azides in solution

The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a), and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitrene 4b. The presence of water does not change the chemistry or kinetics of singlet nitrenes 2b and 3b, but leads to protonation of 4b to produce nitrenium ion 4f. Singlet nitrenes 2b and 3b have lifetimes of 2 ns and 400 ps, respectively, in solution at ambient temperature. The singlet nitrene 4b in acetonitrile has a lifetime of about 800 ps, and reacts with water with a rate constant of 1.9 × 10(8) L·mol(-1)·s(-1) at room temperature. These results indicate that a methoxycarbonyl group at either the para or ortho positions has little influence on the ISC rate, but that the presence of a 2-methoxy group dramatically accelerates the ISC rate relative to the unsubstituted phenylnitrene. An ortho-methoxy group highly stabilizes the corresponding nitrenium ion and favors its formation in aqueous solvents. This substituent has little influence on the ring-expansion rate. These results are consistent with theoretical calculations for the various intermediates and their transition states. Cyclization from the nitrene to the azirine intermediate is favored to proceed toward the electron-deficient ester group; however, the higher energy barrier is the ring-opening process, that is, azirine to ketenimine formation, rendering the formation of the ester-ketenimine (4d') to be less favorable than the isomeric MeO-ketenimine (4d).     

Ultrafast dynamics and excited state spectra of open-chain carotenoids at room and low temperatures

Many of the spectroscopic features and photophysical properties of carotenoids are explained using a three-state model in which the strong visible absorption of the molecules is associated with an S0 (1(1)Ag-) --> S2 (1(1)Bu+) transition, and the lowest lying singlet state, S1 (2(1)Ag-), is a state into which absorption from the ground state is forbidden by symmetry. However, semiempirical and ab initio quantum calculations have suggested additional excited singlet states may lie either between or in the vicinity of S1 (2(1)Ag-) and S2 (1(1)Bu+), and some ultrafast spectroscopic studies have reported evidence for these states. One such state, denoted S*, has been implicated as an intermediate in the depopulation of S2 (1(1)Bu+) and as a pathway for the formation of carotenoid triplet states in light-harvesting complexes. In this work, we present the results of an ultrafast, time-resolved spectroscopic investigation of a series of open-chain carotenoids derived from photosynthetic bacteria and systematically increasing in their number of pi-electron carbon-carbon double bonds (n). The molecules are neurosporene (n = 9), spheroidene (n = 10), rhodopin glucoside (n = 11), rhodovibrin (n = 12), and spirilloxanthin (n = 13). The molecules were studied in acetone and CS2 solvents at room temperature. These experiments explore the effect of solvent polarity and polarizability on the spectroscopic and kinetic behavior of the molecules. The molecules were also studied in ether/isopentane/ethanol (EPA) glasses at 77 K, in which the spectral resolution is greatly enhanced. Analysis of the data using global fitting techniques has revealed the ultrafast dynamics of the excited states and spectral changes associated with their decay, including spectroscopic features not previously reported. The data are consistent with S* being identified with a twisted conformational structure, the yield of which is increased in molecules having longer pi-electron conjugations. In particular, for the longest molecule in the series, spirilloxanthin, the experiments and a detailed quantum computational analysis reveal the presence of two S* states associated with relaxed S1 (2(1)Ag-) conformations involving nearly planar 6-s-cis and 6-s-trans geometries. We propose that in polar solvents, the ground state of spirilloxanthin takes on a corkscrew conformation that generates a net solute dipole moment while decreasing the cavity formation energy. Upon excitation and relaxation into the S1 (2(1)Ag-) state, the polyene unravels and flattens into a more planar geometry with comparable populations of 6-s-trans and 6-s-cis conformations.     

The direct detection of an aryl azide excited state: an ultrafast study of the photochemistry of para- and ortho-biphenyl azide

Ultrafast laser flash photolysis (266 nm) of para- and ortho-biphenyl azide in acetonitrile produces azide excited states that have broad absorption bands centered at 480 nm. The para-biphenyl azide excited singlet state has a lifetime of 100 fs. The excited-state lifetime of the ortho-azide isomer is 450 +/- 150 fs. Decay of the azide excited states is accompanied by the formation of the corresponding known singlet nitrenes (para, lambdamax = 350 nm, ortho, lambdamax = 400 nm). Singlet para-biphenylnitrene is born with excess energy and undergoes vibrational cooling with a time constant of 11 ps to form the long-lived (tau approximately 9 ns) relaxed singlet nitrene. Singlet ortho-biphenylnitrene decays with a lifetime of 16 ps in acetonitrile at ambient temperature.     

Competition between alpha-cleavage and energy transfer in alpha-azidoacetophenones

Molecular modeling demonstrates that the first excited state of the triplet ketone (T1K) in azide 1b has a (pi,pi*) configuration with an energy that is 66 kcal/mol above its ground state and its second excited state (T2K) is 10 kcal/mol higher in energy and has a (n,pi*) configuration. In comparison, T1K and T2K of azide 1a are almost degenerate at 74 and 77 kcal/mol above the ground state with a (n,pi*) and (pi,pi*) configuration, respectively. Laser flash photolysis (308 nm) of azide 1b in methanol yields a transient absorption (lambdamax=450 nm) due to formation of T1K, which decays with a rate of 2.1 x 105 s-1 to form triplet alkylnitrene 2b (lambdamax=320 nm). The lifetime of nitrene 2b was measured to be 16 ms. In contrast, laser flash photolysis (308 nm) of azide 1a produced transient absorption spectra due to formation of nitrene 2a (lambdamax=320 nm) and benzoyl radical 3a (lambdamax=370 nm). The decay of 3a is 2 x 105 s-1 in methanol, whereas nitrene 2a decays with a rate of approximately 91 s-1. Thus, T1K (pi,pi*) in azide 1b leads to energy transfer to form nitrene 2b; however, alpha-cleavage is not observed since the energy of T2K (n,pi*) is 10 kcal/mol higher in energy than T1K, and therefore, T2K is not populated. In azide 1a both alpha-cleavage and energy transfer are observed from T1K (n,pi*) and T2K (pi,pi*), respectively, since these triplet states are almost degenerate. Photolysis of azide 1a yields mainly product 4, which must arise from recombination of benzoyl radicals 3a with nitrenes 2a. However, products studies for azide 1b also yield 4b as the major product, even though laser flash photolysis of azide 1b does not indicate formation of benzoyl radical 3b. Thus, we hypothesize that benzoyl radicals 3 can also be formed from nitrenes 2. More specifically, nitrene 2 does undergo alpha-photocleavage to form benzoyl radicals and iminyl radicals. The secondary photolysis of nitrenes 2 is further supported with molecular modeling and product studies.     

HL-LH2中色素分子间的单重激发态能量传递

采用飞秒时间分辨吸收光谱手段观测了在500和800 nm激发下高光培养的紫色光合细菌Rhodopseu-domonas(Rps). palustris外周捕光天线LH2(HL-LH2)中不同共轭链长类胡萝卜素(Carotenoid, 简称Car)和细菌叶绿素a(Bacteriachlorophyll a, 简称BChl a)的特征吸收光谱. 光谱动力学分析结果表明, HL-LH2中不同Car分子间可能存在复杂的单重激发态能量平衡过程, Car分子同时向BChl a分子发生多途径的单重激发态能量传递, B800主要接受来自Car的S2和S1态能量; B850则主要接受来自长共轭链Car(共轭双键数目n=13)的S1态和B800的激发态能量, 整个能量传递过程在3~5 ps内完成.     

Existence of a new emitting singlet state of proflavine: femtosecond dynamics of the excited state processes and quantum chemical studies in different solvents

Proflavine (3,6-diaminoacridine) shows fluorescence emission with lifetime, 4.6 ± 0.2 ns, in all the solvents irrespective of the solvent polarity. To understand this unusual photophysical property, investigations were carried out using steady state and time-resolved fluorescence spectroscopy in the pico- and femtosecond time domain. Molecular geometries in the ground and low-lying excited states of proflavine were examined by complete structural optimization using ab initio quantum chemical computations at HF/6-311++G** and CIS/6-311++G** levels. Time dependent density functional theory (TDDFT) calculations were performed to study the excitation energies in the low-lying excited states. The steady state absorption and emission spectral details of proflavine are found to be influenced by solvents. The femtosecond fluorescence decay of the proflavine in all the solvents follows triexponential function with two ultrafast decay components (τ(1) and τ(2)) in addition to the nanosecond component. The ultrafast decay component, τ(1), is attributed to the solvation dynamics of the particular solvent used. The second ultrafast decay component, τ(2), is found to vary from 50 to 215 ps depending upon the solvent. The amplitudes of the ultrafast decay components vary with the wavelength and show time dependent spectral shift in the emission maximum. The observation is interpreted that the time dependent spectral shift is not only due to solvation dynamics but also due to the existence of more than one emitting state of proflavine in the solvent used. Time resolved area normalized emission spectral (TRANES) analysis shows an isoemissive point, indicating the presence of two emitting states in homogeneous solution. Detailed femtosecond fluorescence decay analysis allows us to isolate the two independent emitting components of the close lying singlet states. The CIS and TDDFT calculations also support the existence of the close lying emitting states. The near constant lifetime observed for proflavine in different solvents is suggested to be due to the similar dipole moments of the ground and the evolved emitting singlet state of the dye from the Franck-Condon excited state.     

Photoinduced omega-bond dissociation in the higher excited singlet (S2) and lowest triplet (T1) states of a benzophenone derivative in solution

Photochemical properties of photoinduced omega-bond dissociation in p-benzoylbenzyl phenyl sulfide (BBPS) in solution were investigated by time-resolved EPR and laser flash photolysis techniques. BBPS was shown to undergo photoinduced omega-bond cleavage to yield the p-benzoylbenzyl radical (BBR) and phenyl thiyl radical (PTR) at room temperature. The quantum yield (phi(rad)) for the radical formation was found to depend on the excitation wavelength, i.e., on the excitation to the excited singlet states, S2 and S1 of BBPS; phi(rad)(S2) = 0.65 and phi(rad)(S1) = 1.0. Based on the CIDEP data, these radicals were found to be produced via the triplet state independent of excitation wavelength. By using triplet sensitization of xanthone, the efficiency (alpha(rad)) of the C-S bond fission in the lowest triplet state (T1) of BBPS was determined to be unity. The agreement between phi(rad)(S1) and alpha(rad) values indicates that the C-S bond dissociation occurs in the T1 state via the S1 state due to a fast intersystem crossing from the S1 to the T1 state. In contrast, the wavelength dependence of the radical yields was interpreted in terms of the C-S bond cleavage in the S2 state competing with internal conversion from the S2 to the S1 state. The smaller value of phi(rad)(S2) than that of phi(rad)(S1) was proposed to originate from the geminate recombination of singlet radical pairs produced by the bond dissociation via the S2 state. Considering the electronic character of the excited and dissociative states in BBPS showed a schematic energy diagram for the omega-bond dissociation of BBPS.     

Time-resolved two-photon spectroscopy of photosystem I determines hidden carotenoid dark-state dynamics

We present time-resolved fs two-photon pump-probe data measured with photosystem I (PS I) of Thermosynechococcus elongatus. Two-photon excitation (lambda(exc)/2 = 575 nm) in the spectral region of the optically forbidden first excited singlet state of the carotenoids, Car S1, gives rise to a 800 fs and a 9 ps decay component of the Car S1 --> S(n) excited-state absorption with an amplitude of about 47 +/- 16% and 53 +/- 10%, respectively. By measuring a solution of pure beta-carotene under exactly the same conditions, only a 9 ps decay component can be observed. Exciting PS I at exactly the same spectral region via one-photon excitation (lambda(exc) = 575 nm) also does not show any sub-ps component. We ascribe the observed constant of 800 fs to a portion of about 47 +/- 16% beta-carotene states that can potentially transfer their energy efficiently to chlorophyll pigments via the optically dark Car S1 state. We compared these data with conventional one-photon pump-probe data, exciting the optically allowed second excited state, Car S2. This comparison demonstrates that the fast dynamics of the optically forbidden state can hardly be unravelled via conventional one-photon excitation only because the corresponding Car S1 populations are too small after Car S2 --> Car S1 internal conversion. A direct comparison of the amplitudes of the Car S1 --> S(n) excited-state absorption of PS I and beta-carotene observed after Car S2 excitation allows determination of a quantum yield for the Car S1 formation in PS I of 44 +/- 5%. In conclusion, an overall Car S2 --> Chl energy-transfer efficiency of approximately 69 +/- 5% is observed at room temperature with 56 +/- 5% being transferred via Car S2 and probably very hot Car S1 states and 13 +/- 5% being transferred via hot and "cold" Car S1 states.     

Excited-state dynamics of carotenoids in light-harvesting complexes. 1. Exploring the relationship between the S1 and S* states

Dispersed transient absorption spectra collected at variable excitation intensities in combination with time-resolved signals were used to explore the underlying connectivity of the electronic excited-state manifold of the carotenoid rhodopin glucoside in the light-harvesting 2 complex isolated from Rhodopseudomonas acidophila. We find that the S state, which was recently identified as an excited state in carotenoids bound in bacterial light-harvesting complexes, exhibits a different response to the increase of excitation intensity than the S(1) state, which suggests that the models used so far to describe the excited states of carotenoids are incomplete. We propose two new models that can describe both the time-resolved and the intensity-dependent data; the first postulates that S(1) and S* are not populated in parallel after the decay of the initially excited S(2) state but instead result from the excitation of distinct ground-state subpopulations. The second model introduces a resonantly enhanced light-induced transition during excitation, which promotes population to higher-lying excited states that favors the formation of S* over S(1). Multiwavelength target analysis of the time-resolved and excitation-intensity dependence measurements were used to characterize the involved states and their responses. We show that both proposed models adequately fit the measured data, although it is not possible to determine which model is most apt. The physical origins and implications of both models are explored.     

Femtosecond Time-Resolved Stimulated Raman Spectroscopy of the S(2) (1B(u)) Excited State of beta-Carotene

The electronic and vibrational structure of beta-carotene's early excited states are examined using femtosecond time-resolved stimulated Raman spectroscopy. The vibrational spectrum of the short-lived ( approximately 160 fs) second excited singlet state (S(2),1B(u) (+))of beta-carotene is obtained. Broad, resonantly enhanced vibrational features are observed at approximately 1100, 1300, and 1650 cm(-1) that decay with a time constant corresponding to the electronic lifetime of S(2). The temporal evolution of the vibrational spectra are consistent with significant population of only two low-lying excited electronic states (1B(u) (+) and 2A(g) (-)) in the ultrafast relaxation pathway of beta-carotene.     

Time-Resolved Studies of the Excited-State Dynamics of meso-Tetra(hydroxylphenyl)chlorin in Solution

Meso-tetra(hydroxyphenyl)chlorin (m-THPC) is a new photosensitizer developed for potential use in photodynamic therapy (PDT) for cancer treatment. In PDT, the accepted mechanism of tumor destruction involves the formation of excited singlet oxygen via intermolecular energy transfer from the excited triplet-state dye to the ground triplet-state oxygen. Femtosecond transient absorption measurements are reported here for the excited singlet state dynamics of m-THPC in solution. The observed early time kinetics were best fit using a triple exponential function with time constants of 350 fs, 80 ps and > or = 3.3 ns. The fastest decay (350 fs) was attributed to either internal conversion from S2 to S1 or vibrational relaxation in S2. Multichannel time-resolved absorption and emission spectroscopies were also used to characterize the excited singlet and triplet states of the dye on nanosecond to microsecond time scales at varying concentrations of oxygen. The nanosecond time-resolved absorption data were fit with a double exponential with time constants of 14 ns and 250 ns in ambient air, corresponding to lifetimes of the S1 and T1 states, respectively. The decay of the T1 state varied linearly with oxygen concentration, from which the intrinsic decay rate constant, ki, of 1.5 x 10(6) s-1 and the biomolecular collisional quenching constant, kc, of 1.7 x 10(9) M-1 s-1 were determined. The lifetime of the S1 state of 10 ns was confirmed by fluorescence measurements. It was found to be independent of oxygen concentration and longer than lifetimes of other photosensitizers.     

Single-photon spectroscopy of singlet sulfur atoms and the autoionization lifetime measurements of the superexcited singlet states

Single-photon excitation spectra from the lowest singlet (1)D(2) level of sulfur atoms were recorded with a tunable vacuum ultraviolet (VUV) radiation source generated by frequency tripling in noble gases. The photolysis of CS(2) at 193 nm was used to produce the singlet S((1)D(2)) sulfur atoms that were then excited to neutral superexcited states with the tunable VUV radiation. These superexcited states undergo autoionization into the first ionization continuum state of S(+)((4)S(3/2) (o))+e(-), which is not directly accessible from the S((1)D(2)) state via an allowed transition. The excitation spectra were recorded by monitoring the S(+) signal in a velocity imaging apparatus while scanning the VUV excitation wavelength. Three new lines were observed in the spectra which have not been previously reported. The full widths at half maximum (FWHM) of each of the observed transitions were determined by fitting the profiles of each absorption resonances with the Fano formula. Autoionization lifetimes tau of these singlet superexcited states were obtained from FWHM using the Uncertainty Principle. Abnormal autoionization lifetimes were found for the 3s(2)3p(3)((2)D(o))nd((1)D(2)) and the 3s(2)3p(3)((2)D(o))ns((1)D(2)) Rydberg series, in which tau(5d) and tau(7s) are shorter than tau(4d) and tau(6s), respectively. This is contrary to the well-known scaling law of tau(n*) proportional, variantn(*3), which should be followed within a series unless there exist perturbations from other series or new channels open up to which some members of the series can decay. Possible perturbations from the nearby triplet series are suspected for causing the broadening of the 5d and 7s levels.     

An optical-optical double resonance probe of the lowest triplet state of jet-cooled thiophosgene: rovibronic structures and electronic relaxation

The vibrational structure, rotational structure, and electronic relaxation of the "dark" T1 3A2(n,pi*) state of jet-cooled thiophosgene have been investigated by two-color S2<--T1<--S0 optical-optical double resonance (OODR) spectroscopy, which monitors the S2-->S0 fluorescence generated by S2<--T1 excitation. This method is capable of isolating the T1 vibrational structure into a1, b1, and b2 symmetry blocks. The fluorescence-detected vibrational structure of the Tz spin state of T1 shows that the CS stretching frequency as well as the barrier height for pyramidal deformation are significantly greater in the 3A2(n,pi*) state than in the corresponding 1A2(n,pi*) state. The differing vibrational parameters of the T1 thiophosgene relative to the S1 thiophosgene can be attributed to the motions of unpaired electrons that are better correlated when they are in the excited singlet state than when they are in the triplet state of same electron configuration. A set of T1 structural parameters and the information concerning the T1 spin states have been obtained from least-square fittings of the rotationally resolved T1<--S0 excitation spectrum. The nearly degenerate mid R:x and mid R:y spin states are well removed from mid R:z spin component, indicating that T1 thiophosgene is a good example of case (ab) coupling. The decay of the mid R:z spin state of T1 thiophosgene, obtained from time-resolved S2<--T1<--S0 OODR experiment, is characteristic of strong-coupling intermediate-case decay in which an initial rapid decay is followed by recurrences and/or a long-lived quasiexponential decay.     

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

We report a femtosecond time-resolved photoelectron spectroscopy (TRPES) investigation of internal conversion in the first two excited singlet electronic states of styrene. We find that radiationless decay through an S(1)/S(0) conical intersection occurs on a timescale of ～4 ps following direct excitation to S(1) with 0.6 eV excess energy, but that the same process is significantly slower (～20 ps) if it follows internal conversion from S(2) to S(1) after excitation to S(2) with 0.3 eV excess energy (0.9 eV excess energy in S(1)).     

Femtosecond excited-state dynamics of 4-nitrophenyl pyrrolidinemethanol: evidence of twisted intramolecular charge transfer and intersystem crossing involving the nitro group

Ultrafast excited-state relaxation dynamics of a nonlinear optical (NLO) dye, (S)-(-)-1-(4-nitrophenyl)-2-pyrrolidinemethanol (NPP), was carried out under the regime of femtosecond fluorescence up-conversion measurements in augmentation with quantum chemical calculations. The primary concern was to trace the relaxation pathways which guide the depletion of the first singlet excited state upon photoexcitation, in such a way that it is virtually nonfluorescent. Ground- and excited-state (singlet and triplet) potential energy surfaces were calculated as a function of the -NO(2) torsional coordinate, which revealed the perpendicular orientation of -NO(2) in the excited state relative to the planar ground-state conformation. The fluorescence transients in the femtosecond regime show biexponential decay behavior. The first time component of a few hundred femtoseconds was ascribed to the ultrafast twisted intramolecular charge transfer (TICT). The occurrence of charge transfer (CT) is substantiated by the large dipole moment change during excitation. The construction of intensity- and area-normalized time-resolved emission spectra (TRES and TRANES) of NPP in acetonitrile exhibited a two-state emission on behalf of decay of the locally excited (LE) state and rise of the CT state with a Stokes shift of 2000 cm(-1) over a time scale of 1 ps. The second time component of a few picoseconds is attributed to the intersystem crossing (isc). In highly polar solvents both the processes occur on a much faster time scale compared to that in nonpolar solvents, credited to the differential stability of energy states in different polarity solvents. The shape of frontier molecular orbitals in the excited state dictates the shift of electron density from the phenyl ring to the -NO(2) group and is attributed to the charge-transfer process taking place in the molecule. The viscosity dependence of relaxation dynamics augments the proposition of considering the -NO(2) group torsional motion as the main excited-state relaxation coordinate.