Acetone in its lowest excited triplet state: an isotope dependent ODMR study

The lowest excited triplet state T₁ of acetone-h₆ and acetone-d₆ was investigated with a pulsed dye laser equipped Optical Detection of Magnetic Resonance spectrometer. The results obtained for this prototype aliphatic carbonyl compound are discussed with reference to a recent ab initio calculation on formaldehyde. The peculiarities of the acetone T₁ are largely determined by its distinct non-planar geometry: Our data indicate that the carbonyl group is rotated out of the plane defined by the three C-atoms, and the distortion angle is found to be appoximately 38°C, similar to the formaldehyde value. This is a central result of our investigation: All of the observed zero-field splitting parameters, ODMR linewidths, kinetic data, and the deuterium effects can be satisfactorily rationalized with this out-of-plane distortion.     

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.     

Emission spectroscopic and ODMR studies of the lowest excited triplet state of dichlorophenylborane

The triplet state T₁ of dichlorophenylborane (PhBCl₂) has been investigated by optical emission and ODMR spectroscopic methods in order to study the influence of substituents with mesomeric and inductive effects. The zero-field splitting (ZFS) parameters D and E, the selective kinetic rates of radiative and non-radiative deactivation of the triplet sublevels and the phosphorescence spectrum were measured. From the small value of D = 0.1201 cm^?1 a considerable charge transfer admixture to the ³L_a state of benzene has to be assumed. The ratio of the radiative rates shows a distortion of the molecule. Further a heavy atom effect of the chlorine atoms on the in-plane rates of the deactivation of T₁ can be observed.     

Xanthone. I. optical detection of an extremely large sublevel splitting the lowest triplet state

The phosphorescence spectrum of xanthone in n-hexane is resolved into three components, one of which is due to thermally activated emission from a n_π* origin. The other two emissions originate from extremely widely split sublevels of the lowest triplet state, which is of ³ππ* origin. higher energy of T_Lx, and T_1y, and thus below 4K there is thermal depletion of T_1z which has the largest radiative strength. Th consequence of spin-orbit coupling between the T_x and T_y sublevels of the-two very close-lying, lowest triplet states. There are signif mixing of orbital character, a mixing which is governed by spin-orbit coupling rather than vibronic coupling.     

Assignment and analysis of the absorption and emission spectra of the lowest nπ* triplet state in 9,10-anthraquinone

Polarized Zeeman absorption experiments on 9,10-anthraquinone crystals show the lowest triplet state in this molecule to be a g nπ^* state. The gap between this state and the higher u nπ^* state is found to be 410 cm^?1. The phosphorescence spectrum of an isotopically mixed crystal of AQ-h₈ in AQ-d₈ is analyzed in detail and confirms the orbitally forbidden nature of the emitting state. The results are compared with those previously obtained for p-benzoquinone.     

The lowest triplet state of pyrimidine in a crystalline host at 1.2 K. The spin-sublevel emission spectra and their vibrational assignment

Spin-sublevel phosphorescence spectra of pyrimidine in benzene are reported. The spectra related to the in-plane spin axes consist of progressions of totally symmetric bands, whereas that of the third sublevel in addition shows strong non-totally symmetric bands. Assignments are given, and some out-of-plane modes previously in dispute are identified (ν_10b = 808, ν_17b = 960, ν_s = 992 cm^?1, A₂). As a check similar experiments were carried out of pyrimidine incorporated in p-xylene and cyclohexane.     

Molecular packing effects on the optical spectra and triplet dynamics in oligofluorene films

We report on the triplet spectra and dynamics in two types of oligomeric films deposited by two different techniques: thermal evaporation and spin coating. The different molecular arrangement in both films is manifested in a red shift of the absorption, PL, and T1-Tn absorption spectra of the sublimated film relative to the spin-coated one. Triplet recombination dynamics studied with steady-state photoinduced absorption (PA) spectroscopy follow a dispersive bimolecular recombination model away from the trap filling regime. We obtained values for the triplet bimolecular recombination ratio (beta) of 3.4 x 10 (-14) and 1.1 x 10 (-15) cm3 s (-1) for evaporated and spin-coated film, respectively, the difference being attributed to diverse molecular arrangement in both films.     

Position-dependent heavy atom effect in the subrates of the lowest triplet state of dichloronaphthalenes

By means of the microwave-induced delayed phosphorescence (MIDP) technique, the dynamics of the lowest triplet state T₀ of several dichloronaphthalenes in naphthalene and durene are investigated. It is shown that the position dependence is very selective in the nonradiative decay of the spin-sublevels: The out-of-plane spin state is nearly not affected, while the in-plane states are strongly affected. The radiative rates, on the other hand, are not selectively influenced by the position of substitution. Besides, the results show that the dynamics of the lowest triplet state is determined by the type of substitution, rather than by the symmetry of the molecule. The spin—orbit coupling of the in-plane states seems to profit from some distortion the guest molecule experiences in the naphthalene host lattice.     

DFT study of the effect of substituents on the absorption and emission spectra of Indigo

ABSTRACT: BACKGROUND: Theoretical analyses of the indigo dye molecule and its derivatives with Chlorine (Cl), Sulfur (S), Selenium (Se) and Bromine (Br) substituents, as well as an analysis of the Hemi-Indigo molecule, were performed using the Gaussian 03 software package. RESULTS: Calculations were performed based on the framework of density functional theory (DFT) with the Becke 3- parameter-Lee-Yang-Parr (B3LYP) functional, where the 6-31 G(d,p) basis set was employed. The configuration interaction singles (CIS) method with the same basis set was employed for the analysis of excited states and for the acquisition of the emission spectra. CONCLUSIONS: The presented absorption and emission spectra were affected by the substitution position. When a hydrogen atom of the molecule was substituted by Cl or Br, practically no change in the absorbed and emitted energies relative to those of the indigo molecule were observed; however, when N was substituted by S or Se, the absorbed and emitted energies increased.     

A deuterium isotope effect on the lifetime of the second triplet state of naphthalene

From a Stern-Volmer kinetic analysis of the naphthalene-T₂ sensitized reaction of endodicyclopentadiene with benzene as the intermediate excitation carrier, it was concluded that deuterium substitution increases the T₂-lifetime of naphthalene. An isotope effect of 1.4 ± 0.3 was observed for per-deuteronaphthalene.     

不同极性溶剂中2-蒽醌磺酸钠三重态特征瞬态吸收谱及动力学研究

利用纳秒级激光光解瞬态吸收光谱装置－248nm(KrF）激光光解研究了水和乙腈溶液中2－蒽醌磺酸钠激发三重态的瞬态吸收光谱。水溶液中纯将的AQS激发三重态的特征吸收在580nm处；确定了AQS激发三重态的特征吸收普形、范围在水和乙腈溶液中的相似性；2－蒽醌磺酸钠激发三重态的半衰期在乙腈中为10.7μs，在水中却为为0.5μs；测定了2－蒽醌磺酸钠激发三重态衰减动力学参数。     

Optically detected magnetic resonance study of the lowest excited triplet state of aromatic thioketones: Xanthione

The aromatic thioketone xanthione has been investigated by means of the optically detected magnetic resonance (ODMR) technique in a n-hexane matrix at ≈ 1.1 K. It was established that the short-lived red emission, which is characteristic for many thione molecules, is phosphorescence. At high temperatures (77 K) this phosphorescence originates mainly (>80%) from the T₁^z (n, π*) sublevel (k_z^(r) >k_x^(r), k_y^(r). At low temperature (1.1 K) the intersystem crossing following S₂ (π, π*) ← S₀ excitation is a highly spin-sublevel selective process which populates predominantly the T₁^x and T₁^y, levels. Hence, the slow spin—lattice relaxation phosphorescence at low temperature originates from these sublevels. A value of 0.0611 cm^?1 was obtained for the zero-field parameter |E|/hc. A lower limit of 0.66 cm^?1 has been found for the zero-field parameter |D|/hc. This value is considerably larger than those observed for ketones, and it is shown that spin—orbit coupling contributes strongly to the zero-field splitting.     

Computational study of the lowest triplet state of ruthenium polypyridyl complexes used in artificial photosynthesis

The potential energy surfaces of the first excited triplet state of some ruthenium polypyridyl complexes were investigated by means of density functional theory. Focus was placed on the interaction between the geometrical changes accompanying the photoactivity of these complexes when used as antenna complexes in artificial photosynthesis and dye-sensitized solar cells and the accompanying changes in electronic structure. The loss process (3)MLCT --> (3)MC can be understood by means of ligand-field splitting, traced down to the coordination of the central ruthenium atom.     

Phosphorescence properties and kinetics of the lowest triplet state T1 of a series of pyrene derivatives as obtained by ODMR techniques

The experimental results of an ODMR investigation of the radiative and nonradiative properties of the lowest electronically excited triplet state T₁ of a series of pyrene derivatives are presented. The paper gives the highly resolved phosphorescence spectra of 1,2-benzopyrene, naphtho-(2′, 3′ ; 1,2)-pyrene, anthraceno-(2′, 3′; 1, 2)-pyrene, 1,2:6,7-dibenzo-pyrene, 1,2-benzonaphtho-(2′, 3′; 6, 7)-pyrene and 1,2; 4,5-dibenzo-pyrene along with vibrational analyses and — in part — symmetry assignments. The correlation know from the literature between triplet energies and the ZFS-parameter D is discussed in terms of character orders. Three of the molecules exhibit an unusual deactivation behaviour similar to that of 3,4-benzo-pyrene where the out-of-plane level is not the slowest level. Several possibilities to explain this unexpected behaviour are discussed.     

Theoretical study of pyrazolate-bridged dinuclear platinum(II) complexes: interesting potential energy curve of the lowest energy triplet excited state and phosphorescence spectra

Four kinds of 3,5-dialkylpyrazolate(R2pz)-bridged dinuclear platinum(II) complexes [Pt2(mu-R2pz)2(dfppy)2] (dfppy=2-(2,4-difluorophenyl)pyridine; R2pz=pyrazolate in 1, 3,5-dimethylpyrazolate in 2, 3-methyl-5- tert-butylpyrazolate in 3, and 3,5-bis(tert-butyl)pyrazolate in 4) were theoretically investigated by the DFT(B3PW91) method. The Stokes shift of their phosphorescence spectra was discussed on the basis of the potential energy curve (PEC) of the lowest energy triplet excited state (T1). This PEC significantly depends on the bulkiness of substituents on pz. In 1 and 2, bearing small substituents on pz, one local minimum is present in the T1 state besides a global minimum. The local minimum geometry is similar to the S0-equilibrium one. The T1 state at this local minimum is characterized as the pi-pi* excited state in dfppy, where the dpi orbital of Pt participates in this excited state through an antibonding interaction with the pi orbital of dfppy; in other words, this triplet excited state is assigned as the mixture of the ligand-centered pi-pi* excited and metal-to-ligand charge transfer excited state ((3)LC/MLCT). The geometry of the T1-global minimum is considerably different from the S0-equilibrium one. The T1 state at the global minimum is characterized as the triplet metal-metal-to-ligand charge transfer ((3)MMLCT) excited state, which is formed by the one-electron excitation from the dsigma-dsigma antibonding orbital to the pi* orbital of dfppy. Because of the presence of the local minimum, the geometry change in the T1 state is suppressed in polystyrene at room temperature (RT) and frozen 2-methyltetrahydrofuran (2-MeTHF) at 77 K. As a result, the energy of phosphorescence is almost the same in these solvents. In fluid 2-MeTHF at RT, on the other hand, the geometry of the T1 state easily reaches the T1-global minimum. Because the T1-global minimum geometry is considerably different from the S0-equilibrium one, the phosphorescence occurs at considerably low energy. These are the reasons why the Stokes shift is very large in fluid 2-MeTHF but small in polystyrene and frozen 2-MeTHF. In 3 and 4, bearing bulky tert-butyl substituents on pz, only the T1-global minimum is present but the local minimum is not. The electronic structure of this T1-global minimum is assigned as the (3)MMLCT excited state like 1 and 2. Though frozen 2-MeTHF suppresses the geometry change of 3 and 4 in the T1 state, their geometries moderately change in polystyrene because of the absence of the T1-local minimum. As a result, the energy of phosphorescence is moderately lower in polystyrene than in frozen 2-MeTHF. The T1-global minimum geometry is much different from the S0-equilibrium one in 3 but moderately different in 4, which is interpreted in terms of the symmetries of these complexes and the steric repulsion between the tert-butyl group on pz and dfppy. Thus, the energy of phosphorescence of 3 is much lower in fluid 2-MeTHF than in frozen 2-MeTHF like 1 and 2 but that of 4 is moderately lower; in other words, the Stokes shift in fluid 2-MeTHF is small only in 4.     

Secondary kinetic isotope effect on the photoenolization of triplet o-methylanthrones. A microcanonical transition state theory calculation

The energy profile for the tautomerization reaction of 1,4-dimethylanthrone in the first triplet electronic state obtained through electronic calculations (B3LYP/ 6-31G(d)) is used to calculate the rate constants for the process at a wide range of energies using a modified RRKM microcanonical statistical formalism that takes into account tunneling. Through partial or total substitution of the hydrogen atoms of the methyl groups by deuterium atoms, it is possible to evaluate different primary and secondary kinetic isotope effects (KIE). These results can be compared with experimental data for these processes taking place in solid matrix at extremely low temperatures (4-50 K). Such a comparison allows us to conclude that the reaction is taking place at energies just slightly below (around 0.5 kcal/mol) the adiabatic potential energy barrier, a result that was previously found for other related molecules so that this mechanism may be extended to the photoenolization of other o-aryl methyl ketones. Analysis of the different factors contributing to the primary and secondary KIEs discloses that at energies not far below the adiabatic barrier, the tunneling effect is not the only factor that accounts for the large KIE but the differences in the energy level distribution upon isotopic substitution may be the predominant factor at a certain range of negative energies (this is especially so for the case of primary KIE). At positive energies (above the barrier) the levels factor is always the dominant factor in the total KIE.     

Theoretical study of the absorption and emission spectrum and non-adiabatic excited state dynamics of gas-phase xanthone

The ground, singlet, and triplet excited state structures (S₁, S₂, T₁, and T₂) of xanthone have been calculated and characterized in the adiabatic representation by using time-dependent density functional theory (TDDFT). However, the fast intramolecular transition mechanisms of xanthone are still under debate, and so we perform non-adiabatic excited state dynamics of the photochemistry of xanthone gas phase and find that it follows El-Sayed's rule. Electronic transition mechanism of xanthone is sequential from the S₂ state: the singlet internal conversion (IC) time from S₂ (¹ππ*) to S₁ (¹nπ*) is 3.85 ps, the intersystem crossing (ISC) from S₁ (¹nπ*) to T₂ (³ππ*) takes 4.76 ps, and the triplet internal conversion from T₂ (³ππ*) to T₁ (³nπ*) takes 472 fs. The displaced oscillator, Franck–Condon approximation, and one-photon excitation equations were used to simulate the absorption spectra of S₀ → S₂ transition, with v₅₅ being most crucial for S₀ structure; the fluorescence spectra of S₁ → S₀ transition with v₄₇ for S₁; and the phosphorescence spectra of T₁ → S₀ transition with v₄ for T₁. Our method can reproduce the experimental absorption, fluorescence, and phosphorescence spectra of gas-phase xanthone.     

ODMR in zero field of the photoexcited triplet state of naphthalene and quinoxaline dissolved in argon matrices

ODMR of zero-field transitions in the triplet states of naphthalene and quinoxaline in an argon host are reported. Excitation with a Hg are leads to linewidths considerably smaller than those obtained for the same molecules dissolved in glassy matrices. In naphthalene selective laser excitation reduces the linewidth to a value almost equal to those observed in single crystals.     

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.