Time‐resolved resonance Raman and density functional theory study of the photochemistry of 4‐benzoylpyridine in acetonitrile and 2‐propanol

A nanosecond time‐resolved resonance Raman (ns‐TR³) spectroscopic investigation of the intermolecular hydrogen‐abstraction reaction of the triplet state of 4‐benzoylpyridine (4‐BPy) in 2‐propanol solvent is reported. The TR³ results reveal a rapid hydrogen abstraction (<10 ns) by the 4‐BPy triplet state (nπ*) with the 2‐propanol solvent, leading to formation of a 4‐BPy ketyl radical and an associated dimethyl ketyl radical partner from the solvent. The recombination of these two radical species occurs with a time constant about 200 ns to produce a para‐N‐LAT (light absorbing transient). The structure, major spectral features, and identification of the ketyl radical and the para‐N‐LAT coupling complex have been determined and confirmed by comparison of the TR³ results with results from density functional theory (DFT) calculations. A reaction pathway for the photolysis of 4‐BPy in 2‐propanol deduced from the TR³ results is also presented. The electron‐withdrawing effect of the heterocyclic nitrogen for 4‐BPy on the triplet state makes it have a significantly higher chemical reactivity for the hydrogen abstraction with 2‐propanol compared to the previously reported corresponding benzophenone triplet reaction under similar reaction conditions. In addition, the 4‐BPy ketyl radical reacts with the dimethyl ketyl radical to attach at the para‐N atom position of the pyridine ring to form a cross‐coupling product such as 2‐[4‐(hydroxy‐phenyl‐methylene)‐4h‐pyridin‐1‐yl]‐propan‐2‐ol instead of attacking at the para‐C atom position as was observed for the corresponding benzophenone reaction reported in an earlier study. Copyright © 2008 John Wiley & Sons, Ltd.     

Influence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: a time‐resolved resonance Raman and density functional theory study

A nanosecond time‐resolved resonance Raman (ns‐TR³) spectroscopic investigation of the photoreduction reactions and ability of several chloro‐substituted benzophenone (Cl‐BP) triplets is described. The TR³ results show that the 3‐chlorobenzophenone (3‐Cl‐BP), 4‐chlorobenzophenone (4‐Cl‐BP) and 4,4′‐dichlorobenzophenone (4,4′‐dichloro‐BP) triplets exhibit similar hydrogen abstraction ability with the parent BP triplet. In 2‐propanol, the 3‐Cl‐, 4‐Cl‐ and 4,4′‐dichloro‐diphenylketyl (DPK) radicals were observed and they appear to react with dimethylketyl radicals at the para‐position to form a light absorption transient species. These transient species were characterized with TR³ spectra, and identified with the help of results from density functional theory calculations. In an acetontitrile/water (MeCN:H₂O) 1:1 mixed solvent, these DPK radicals were also observed but with slower formation rates. However, the 2‐Cl‐DPK radical was observed to form with a lower yield and a significantly slower formation rate than the other chloro‐substituted benzophenones examined here in 2‐propanol under the same experimental conditions. These results reveal that the 2‐chloro substituent reduces the hydrogen abstraction ability of the substituted BP triplet, which was not as expected based on the assumption that the electron‐withdrawing group could increase its photoreduction ability. This unusual ortho effect of the chlorine substitution is briefly discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Solvent effects on the structure of the triplet excited state of xanthone: a time‐resolved resonance Raman study

Solvent effects, especially intermolecular hydrogen bonding, play a central role in the photophysics and photochemistry of aromatic ketones. To gain insight into the solute–solvent interactions and their implications for structure and reactivity, we studied xanthone (XT) in two different solvents of similar dipolarity: acetonitrile (ACN; aprotic) and methanol (MeOH; protic), using time‐resolved resonance Raman (TR³) spectroscopy in conjunction with time‐dependent density functional theory calculations. Raman excitation profiles of XT in ACN followed the triplet‐triplet absorption band with a shoulder at the blue end, but for MeOH, they followed the triplet‐triplet absorption band quite closely; therefore, we propose that the resonance enhancement of Raman peaks are from two states in ACN and from a single state in the MeOH solvent. Furthermore, a resonance Raman peak at 614 cm⁻¹ (a₂ symmetry) that appeared in ACN but not in the MeOH solvent has been identified as a vibronic active mode that could be involved in coupling the two lowest 1³ππ* (1³A₁) and 1³nπ* (1³A₂) excited states. This was further confirmed by depolarization ratio measurements of some of the representative TR³ peaks in ACN, which showed a depolarized intensity for the 614 cm⁻¹ peak while the other peaks were polarized. Interestingly, we also observed blue shifting of some of the vibrational frequencies of XT in the 1³ππ* state compared with the ground state with increasing solvent polarity. This anomalous blue shift casts doubt on the general use of the resonance canonical structure to explain the structure of the excited states. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet states of XT separate them further in energy and that this can contribute to its low reactivity towards H atom abstraction in protic solvents. Copyright © 2016 John Wiley & Sons, Ltd.     

Decay Dynamics of 3‐methyl‐3‐pentene‐2‐one from the light absorbing S2(ππ*) state ‐ Resonance Raman Spectroscopy and CASSCF Study

The photophysics of 3‐methyl‐3‐pentene‐2‐one (3M3P2O) after excitation to the S₂(ππ*) electronic state were studied using the resonance Raman spectroscopy and complete active space self‐consistent field (CASSCF) method calculations. The A‐band resonance Raman spectra were obtained in cyclohexane, acetonitrile, and methanol with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of 3M3P2O. The B3LYP‐TD/6‐31++G(d, p) computation was carried out to determine the relative A‐band resonance Raman intensities of the fundamental modes, and the result was used to reproduce the corresponding fundamental band intensities of the 223.1 nm resonance Raman spectrum and thus to examine whether the vibronic‐coupling existed in Franck‐Condon region or not. CASSCF calculations were carried out to determine the minimal singlet excitation energies of S_{1, FC}, S_1,min (nπ*), S_{2, FC}, S_2,min (ππ*), the transition energies of the conical intersection points S_n/S_π, S_n/S₀, and the optimized excited state geometries as well as the geometry structures of the conical intersection points. The A‐band short‐time structural dynamics and the corresponding decay dynamics of 3M3P2O were obtained by the analysis of the resonance Raman intensity pattern and CASSCF computations. It was revealed that the initial structural dynamics of 3M3P2O was towards the simultaneous C₃=C₄ and C₂=O₇ bond elongation, with the C₃=C₄ bond length lengthening greater at the very beginning, whereas the C₂=O₇ bond length changing greater at the later evolution time before reaching the CI(S₂/S₁) conical intersection point. The decay dynamics from S₂(ππ*) to S₁(nπ*) via S₂(ππ*)/S₁(nπ*) in singlet realm and from S₁(nπ*) to T₁(nπ*) via ISC[S₁(nπ*)/T₂(ππ*)/T₁(nπ*)] in triplet realm are proposed. Copyright © 2014 John Wiley & Sons, Ltd.     

Optical and time-resolved EPR studies of the excited states of azastilbenes and their protonated cations

The effects of protonation on the excited states oftrans-3-styrylpyridine (StP) andtrans-4,4′-dipyridylethylene (DPE) have been studied through measurements of the time-resolved electron paramagnetic resonance (EPR), ultraviolet absorption, and fluorescence spectra in methanol-water mixtures at 77 K. The assignment of the transient EPR signals was carried out with the aid of the stretched poly(vinyl alcohol) films method. From the analysis of these spectra it is concluded that the single protonation appears to have little effect on the zero-field splitting parameters and the anisotropy in the sublevel populating rates of the lowest excited triplet (T₁) states of StP and DPE. However, the decay rate constants of the fluorescent states decrease and fluorescence quantum yields increase on single protonation. These experimental results suggest that the single protonation causes a decrease in the intersystem crossing (ISC) rates for the three T₁ sublevels. These results are explained in terms of the vibronic mixing between the¹nπ* and¹ππ* states in the lowest excited singlet state. The assignment of StP to the specified conformer was carried out through the analysis of the anisotropic ISC processes.     

Sub‐picosecond Raman spectrometer for time‐resolved studies of structural dynamics in heme proteins

We describe a pump–probe Raman spectrometer based on a femtosecond Ti:sapphire laser, an optical parametric generator and two optical parametric amplifiers for time‐resolved studies, with emphasis on the structural dynamics in heme proteins. The system provides a 100‐fs pump pulse tunable in the range 500–600 nm and a transform‐limited sub‐picosecond probe pulse tunable in the range 390–450 nm. The spectrometer has spectral (25 cm⁻¹) and temporal (∼0.7 ps) resolutions which constitute an effective compromise for identifying transient heme protein species and for following their structural evolution by spontaneous Raman scattering in the time range 0.5 ps to 2 ns. This apparatus was applied to time‐resolved studies of a broad range of heme proteins, monitoring the primary dynamics of photoinduced heme coordination state and structural changes, its interaction with protein side‐chains and diatomic gaseous ligands, as well as heme vibrational cooling. The treatment of transient Raman spectra is described in detail, and the advantages and shortcomings of spontaneous resonance Raman spectroscopy for ultrafast heme proteins studies are discussed. We demonstrate the efficiency of the constructed spectrometer by measuring Raman spectra in the sub‐picosecond and picosecond time ranges for the oxygen‐storage heme protein myoglobin and for the oxygen‐sensor heme protein FixLH in interaction with the diatomic gaseous ligands CO, NO, and O₂. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of chlorine substitution on triplet state structure of thioxanthone: A time‐resolved resonance Raman study

Substitution plays an important role in determining the triplet state reactivity. In this paper, we have studied the effect of chlorine substitution on the triplet state structure and the reactivity of thioxanthone (TX). We have employed time‐resolved resonance Raman technique to understand the structure of the lowest triplet excited state of 2‐chlorothioxanthone (CTX). The experimental findings have been corroborated with the computational results using density functional theory. Akin to the parent compound (TX), coexistence of two lowest triplet states has been observed in case of CTX, which has been substantiated using resonant probe wavelength dependence study. The relative contribution of ³n–π* to ³π–π* to the equilibrated triplet state has been found to be more for CTX compared to TX suggesting increase in the triplet state reactivity after the substitution. The above observation has been further supported by the flash photolysis experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Time‐resolved Raman studies on Al2O3: Cr3+: lifetime measurements of the excited‐state transition Ē → 2Ā

A time‐resolved intensified charge coupled device‐based Raman microspectrometer system dedicated to the study of solid samples is described, offering good optical, temporal and spatial resolution. The advantages of this approach are demonstrated on Al₂O₃:Cr³⁺, obtaining for the first time the temporal evolution of the excited state transition Ē → 2Ā. Moreover, the time dependence of the luminescence due to the chromium ion was also determined by the same Raman device. Copyright © 2010 John Wiley & Sons, Ltd.     

Excited‐state deactivation channels via internal conversions in two position isomers of hydroxy‐methyl‐pyridine: a theoretical study

Two position isomers of hydroxy‐methyl‐pyridine (3‐hydroxy‐2‐methyl‐pyridine and 2‐hydroxy‐3‐methyl‐pyridine) were studied theoretically at the BLYP level of theory in order to find mechanisms explaining the excited‐state deactivations of isomers through ring puckering and “ethylene‐like” conical intersections. The study aims also to clarify the mechanisms of the ground‐state proton transfers. Three conical intersections S₀/S₁ for each isomer were found, which are accessible through the ¹ππ* excited states. In both isomers, there is a ¹ππ* excited‐state reaction path, which leads, in a completely barrierless manner, to the one of the conical intersections S₀/S₁. Copyright © 2015 John Wiley & Sons, Ltd.     

Time-resolved EPR and ODMR studies on the lowest excited triplet states of α-silyl and α-germyl ketones

Sublevel properties of the lowest excited triplet (T¹) nπ* states of α-silyl and α-germyl ketones were examined by means of ODMR, time-resolved EPR and optical spectroscopy. The EPR parameters, D, E and g, population ratios, and triplet lifetimes were obtained. The D value and the triplet lifetime varied among the molecules. In contrast the E value and population ratio remains nearly the same. These properties together with their solvent dependence and emission properties are interpreted in terms of spin-orbit couplings between T₁ (nπ*) and higher S₁ (nπ*), T₂ (ππ*) and S₂ (ππ*) states. An origin of the remarkable red-shifts of ^1,3 (π*) are discussed based on a model of delocalized n, π and π* electrons over the Si and Ge atoms. This model is also consistent with all the triplet properties obtained.     

Time‐resolved investigation of the ν1 ro‐vibrational Raman band of H2CO with fs‐CARS

The technique of femtosecond time‐resolved coherent anti‐Stokes scattering (fs‐CARS) is used to investigate the strongly perturbed ν₁ ro‐vibrational Raman band of formaldehyde (H₂CO). The time‐dependent signal is simulated using a ‘Watson‐’Hamiltonian in A‐type reduction and Raman theory for asymmetric rotors. The results are compared with the experimental data. The fs‐CARS method measures the evolution of the polarization in a molecular ensemble via superposition of many states and is sensitive to spectral irregularities or line shifts of the involved transitions. ‘Coriolis’ interactions play a major role in the analysis of the ν₁ band of formaldehyde. We successfully simulate the fs‐CARS transient signal from the ν₁ band of formaldehyde including a model for multiple ‘Coriolis’ interactions, without the necessity of describing the complete interaction between all the vibrational levels. ‘Coriolis’ coupling coefficients and energy shifts are derived from the experiment by a least‐square fit. The results are discussed and compared to literature values. Copyright © 2006 John Wiley & Sons, Ltd.     

Two-laser two-color time-resolved EPR study on higher-excited-state triplet-singlet intersystem crossing of porphyrins and phthalocyanines

Photoinduced effects on the electron spin polarization (ESP) in the lowest excited triplet (T₁) states of porphyrins (PORs) and phthalocyanines (PCs) have been observed with a two-color time-resolved (TR) electron paramagnetic resonance (EPR) technique in a glassy matrix at low temperatures. On single-color excitation with the wavelengths of the ground state absorptions of PORs and PCs, polarized EPR spectra due to the corresponding T₁ state were observed. The polarization patterns match well with interpretation as anisotropic intersystem crossing (ISC) induced by the spinorbit coupling between the singlet excited (S₁) and the triplet states. In contrast, two-color excitation led to a change of the phase of the T₁ state polarization pattern to the opposite. The observed ESP in the T₁ state resulting from the excitation to the upper triplet state (T _n ) was interpreted in terms of anisotropic ISC between the T _n and S₁ states. From the analysis of the ESP, changes in the quantum yields of the reverse ISC processes were determined at different temperatures. The results could be best interpreted by the existence of thermal pathways with small activation energy in the relaxation processes.     

Intersystem crossing in oligothiophenes studied by fs time-resolved spectroscopy

High triplet quantum yields of more than 90% for bithiophene and terthiophene have to be connected with very fast and effective formation of triplets after excitation. We studied these processes with fs pump–probe spectroscopy. The time behaviour of transient optical spectra within the singlet and triplet manifold was examined for bi- and terthiophene (2T and 3T) in solution. For 2T we used two-photon absorption for excitation. We found transient spectra of the excited singlet state, the triplet state and that of radical cations. The kinetics of the excited-state absorption was described by a bi-exponential function. Additionally we observed formation and recombination of radical cations. The recombination is connected with triplet formation. Both processes could be described by a time constant of 62 ps±9 ps. For 3T we found a dependence of the processes on excitation energy using one-photon absorption. The triplet quantum yield increased with higher excitation energy. The kinetics becomes bi-exponential with increasing amplitude of the short time constant of 2 ps at increasing excitation energy. The main reasons for the effective intersystem crossing (ISC) in both oligothiophenes are – besides the high spin-orbit coupling factor introduced by the sulphur atom – the almost isoenergetic positions of the S ₁ and T ₂ states, detected by PD-PES [1]. At higher photon excitation energy for 3T above the band gap an additional channel for ISC was detected. We believe that during the geometric change from the non-relaxed non-planar to the relaxed planar excited state S ₁, ultrafast intersystem crossing takes place. Received: 6 December 1999 / Published online: 2 August 2000     

Features of dual fluorescence of 1, 2, 3, 4- tetrahydroisoquinoline

In polar and nonpolar solvents, tetrahydroisoquinoline emits S₂ (ππ¹) → S₀ and S₁ (ππ¹) → S₀ dual fluorescence and T₁ (ππ¹) → S₀ phosphorescence on S₂ (ππ¹) ← S₀ excitation. When excited by S₁ (ππ¹) ← S₀ the molecule yields S₁ (ππ¹) → S₀ fluorescence and T₁ (ππ¹) → S₀ phosphorescence in nonpolar solvent but only fluorescence in polar solvents. Probable participation of intermediate S₁ (nπ¹), T₁(nπ¹) states in intersystem crossing and internal conversion processes and its significance in interpreting the results are discussed.     

Shifts of g Values in the Excited Triplet States of Metal Complexes Studied by Time-Resolved W-band EPR

A highly time-resolved high-frequency/high-field W-band electron paramagnetic resonance (EPR) (ν ~ 94 GHz) is a powerful technique to determine small g anisotropies of transient paramagnetic species. We applied this method to studies of the lowest excited triplet (T₁)³ ππ* states in metal complexes such as a platinum (Pt) diimine complex and metal (Zn and Mg) porphines in rigid glasses. From the analyses of time-resolved EPR spectra, g anisotropies were obtained as g _z  = 2.0048, g _x  = g _y  = 2.0035 for Pt(b-iq)(CN)₂ (b-iq = 3,3′bi-isoquinoline) and g _z  = 1.9968, g _x  = g _y  = 2.0022 for zinc tetraphenylporphine (ZnTPP). No measurable anisotropies were found for magnesium (Mg) TPP. The g values of the Pt complex are larger than g _e (=2.0023, g value of free electron) and that g _z of ZnTPP is smaller than g _e. These results were interpreted in terms of the nature of the perturbed states: the higher triplet ππ′* state mixes with T₁(ππ*) via spin–orbit coupling in ZnTPP. In contrast, the higher triplet dπ* state is involved in this coupling for the Pt complex. Thus, the nature of the perturbed state can be distinguished from the anisotropic g values of the T₁(ππ*) state.     

Dissection of dispersed off‐resonant femtosecond degenerate four‐wave mixing of O2

Simultaneous time and frequency detection in off‐resonant femtosecond degenerate four‐wave mixing (fs‐DFWM) experiments displays spectral features that are covered in standard, nondispersed, frequency‐integrated measurements. The application of laser fields with finite bandwidths, narrower than or comparable to the rotational Raman bands, affects the observed coherent signals. Information available from such experiments is split between the time and frequency domains and an improved measurement necessitates a combined detection. Rotational recurrences of oxygen (O₂), measured by dispersed fs‐DFWM at room temperature, exhibit spectral characteristics, using 800‐nm laser pulses with ∼100 fs duration. Analysis of the detected signals in both dimensions incorporating temporal and spectral trends can assist in the extraction and interpretation of chemicophysical quantities from the experiment. The dispersed recurrent signals are in accordance with simulations. Copyright © 2011 John Wiley & Sons, Ltd.     

Studies of the temperature dependence of the phosphorescence spectra and decay rates of aromatic carbonyl molecules in mixed organic crystals

The temperature dependence of the phosphorescence spectra, decay rates and the S ₀ → T ₂(³ nπ*) absorption spectra were studied for aromatic carbonyl molecules in mixed organic crystals. The energy separation, ΔE_T , between the ³ ππ* lowest excited triplet (T ₁) states and the higher ³ π ^* states (T ₂) was estimated for several systems from the temperature dependence of the phosphorescence spectra and decay rates. It was found that the decay rates of the aromatic carbonyl molecules in the mixed crystal systems studied are determined by (1) thermal population to the ³ nπ* states and (2) increased radiationless transition rates at higher temperatures.     

Pump power dependence in resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy (FSRS) has emerged as a powerful new technique that is capable of obtaining resonance Raman spectra of fluorescent species and transient photochemical intermediates. Unlike related transient infrared absorption techniques, the FSRS signal is quite sensitive to the laser power utilized in the vibrational probing event. In particular, FSRS spectra are highly sensitive to the intensity of the picosecond Raman‐pump pulse. We have measured the power dependence of the FSRS signal using pulse energies from ~10⁻⁹ to ~10⁻⁵ J and molecules with a range of molar absorptivities at the Raman‐pump wavelength of 400 nm, including β‐carotene (ε₄₀₀ = 58 300 M⁻¹ cm⁻¹), para‐nitroaniline (17 800 M⁻¹ cm⁻¹), nitronaphthalene (247 M⁻¹ cm⁻¹) and ferrocene (57 M⁻¹ cm⁻¹). We show that for strongly absorbing molecular systems, such as β‐carotene and para‐nitroaniline, the ground‐state (GS) FSRS signal actually decreases with increasing pump power at pump fluences above ~10⁻² J cm⁻², due to depletion of the GS population. However, for weakly absorbing species like nitronaphthalene and ferrocene, the signal increases linearly with increasing pump fluence until ~0.5 J cm⁻², at which point two‐photon absorption by the solute induces nonlinear absorption of the pump pulse and attenuation of the FSRS signal. The data are quantitatively simulated with a photophysical kinetic model, and the results are analyzed to provide simple guidelines for acceptable Raman‐pump powers in resonance FSRS experiments. The acceptable Raman‐pump power is proportional to the focused beam area and depends inversely on the sample's molar absorptivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Radical species generation and their lifetime extension by a femtosecond and nanosecond dual-laser system

For many material processes, desired radical species at excited states are produced which interact with a given substrate for a certain period of time allowing chemical reactions between them to occur and complete. Hence, it is important to maintain the population of the excited radical species for an extended period of time, i.e., their lifetime, which is defined as the time for emission intensity to decay to 1/e of the initial intensity. In this study, a femtosecond–nanosecond (fs–ns) dual-laser system was employed to generate desired radical species via the fs laser and, then, to extend the lifetime of the radical species by the ns laser with different time delays between the two fs–ns laser pulses. The proposed method is demonstrated for a N₂–CO₂ mixture with CN as the radical species. The results show that the lifetime of CN radical species can be significantly extended, particularly the (3, 3) spectral line which was extended from 30 to 200 ns. By using a wavelength-tunable ns laser, the lifetime of most radical species can be extended which may increase the process efficiency for many material processes.     

A New Laser Photochemical Process for Isotope Enrichment

Selective laser excitation of a specific isotopic species to its lowest electronic singlet (S₁) and triplet (T₁) states respectively, then followed by a chemical reaction for isotope separation is examined theoretically. It is found that the direct excitation to T₁ state from ground state (S₀) is an unique excitation channel for obtaining a controllable chemical reaction and for achieving a high isotope separation factor. This is due to the following important facts: 1) Resonant energy transfer from a selectively excited triplet isotopic species to an unexcited species of the other isotope present in the mixture is missing (or is very small); 2) The lifetime of the T₁ state is normally longer than that of the S₁ state; 3) There is no intersystem crossing channel that exists for the deactivation of excited isotopic species from T₁ state.

Numerical calculation is performed for the chlorine isotope separation in a mixture of thiophosgene (0.5 torr) and diethoxyethylene (1.5 torr). The result indicates that the isotopic enrichment factor is at least 2.5 × 10³ times larger for selective T₁ excitation than that for S₁ excitation.