Excited‐state structural dynamics and vibronic coupling of 1,3‐dithiole‐2‐thione—resonance Raman spectroscopy and density functional theory calculation study

1,3‐Dithiole‐2‐thione (DTT) was synthesized and characterized using NMR, FT‐Raman, FT‐IR, UV spectroscopies. Resonance Raman spectra (RRs) were obtained with 341.5, 354.7 and 368.9 nm excitation wavelengths and density functional calculations were done to elucidate the electronic transitions and the RRs of DTT in cyclohexane solution. The RRs indicate that the Franck‐Condon region photodynamics is predominantly along the CS stretch+ H‐CC‐H scissor υ₄, accompanied by the H‐CC‐H scissor υ₃, S‐C‐S symmetric stretch υ₆, CC stretch υ₂, and overtone of the non‐totally symmetric SC‐S2 out‐of‐plane deformation 2υ₁₁. The excited‐state dynamics and the force constant of CS stretch calculated by the RRs were discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Resonance Raman spectra and excited state structural dynamics of ethylene trithiocarbonate in the A‐ and B‐band absorptions

A‐ and B‐band resonance Raman spectra were acquired for ethylene trithiocarbonate in cyclohexane solution. The results indicate that the S₃ state structural dynamics is mostly along vibrational motions of the CS stretch υ₁₁, while the S₄ state one has motions mainly via the S C S symmetric stretch υ₁₈, CS stretch υ₁₁, and the H C H rock + S C S antisymmetric stretch υ14 reaction coordinates. The very different excited state structural dynamics were briefly discussed in terms of vibronic couplings using local symmetry point group. Copyright © 2009 John Wiley & Sons, Ltd.     

Resonance Raman intensity analysisof the excited‐state photochemical dynamicsof dimethyl 1,3‐dithiole‐2‐thione‐4,5‐dicarboxylate in the A‐band absorption

Dimethyl 1,3‐dithiole‐2‐thione‐4,5‐dicarboxylate (DDTD) was synthesized and characterized using NMR, Fourier transform (FT)‐Raman, Fourier transform‐infrared (FT‐IR) and UV spectroscopies. Resonance Raman spectra (RRs) were obtained with 341.5, 354.7 and 368.9 nm excitation wavelengths and density functional calculations were carried out to elucidate the π (S C S) →π* (S C S) electronic transitions and the RRs of DDTD in cyclohexane solution. The RRs indicate that the Franck–Condon region photo dynamics have a multidimensional character with motion predominantly along the CS stretch and the C S symmetric stretch modes in the five‐member heterocycle. A preliminary resonance Raman intensity analysis was carried out and the results for DDTD were compared with previously reported results for 1,3‐dithiole‐2‐thione (DTT). Differences and similarities of the spectra in terms of molecular symmetry and electron density are also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Solvent‐dependent structural dynamics of 2(1H)‐pyridinone in light absorbing S4(ππ*) state

The B‐band resonance Raman spectra of 2(1H)‐pyridinone (NHP) in water and acetonitrile were obtained, and their intensity patterns were found to be significantly different. To explore the underlying excited state tautomeric reaction mechanisms of NHP in water and acetonitrile, the vibrational analysis was carried out for NHP, 2(1D)‐pyridinone (NDP), NHP–(H₂O)_n (n = 1, 2) clusters, and NDP–(D₂O)_n (n = 1, 2) clusters on the basis of the FT‐Raman experiments, the B3LYP/6‐311++G(d,p) computations using PCM solvent model, and the normal mode analysis. Good agreements between experimental and theoretically predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands in both the FT‐Raman and the resonance Raman spectra. The results indicated that most of the B‐band resonance Raman spectra in H₂O was assignable to the fundamental, overtones, and combination bands of about ten vibration modes of ring‐type NHP–(H₂O)₂ cluster, while most of the B‐band resonance Raman spectra in CH₃CN was assigned to the fundamental, overtones, and combination bands of about eight vibration modes of linear‐type NHP–CH₃CN. The solvent effect of the excited state enol‐keto tautomeric reaction mechanisms was explored on the basis of the significant difference in the short‐time structural dynamics of NHP in H₂O and CH₃CN. The inter‐molecular and intra‐molecular ESPT reaction mechanisms were proposed respectively to explain the Franck–Condon region structural dynamics of NHP in H₂O and CH₃CN.Copyright © 2015 John Wiley & Sons, Ltd.     

Structural dynamics of 4‐pyrimidone in lower‐lying excited States

The structural dynamics of 4‐pyrimidone (4PMO) in the A‐ and B‐band absorptions was studied by using the resonance Raman spectroscopy combined with quantum chemical calculations to better understand whether the excited state intramolecular proton‐transfer (ESIPT) reaction occurs in Franck–Condon regions or not. The transition barrier for the ground state proton‐transfer tautomerization reaction between 3(H) (I) and hydroxy (II) was determined to be 165 kJ·mol⁻¹ in vacuum on the basis of the B3LYP/6‐311++G(d,2p) level of theory calculations. Two ultraviolet absorption bands of 4PMO were, respectively, assigned as π_H→π*_L and π_H→π*_L+1 transitions. The vibrational assignments were done on the basis of the Fourier transform (FT)‐Raman and FT‐infrared (IR) measurements, the density‐functional theory computations and the normal mode analysis. The A‐ and B‐band resonance Raman spectra of 4PMO were measured in water, methanol and acetonitrile. The structural dynamics of 4PMO was obtained through the analysis of the resonance Raman intensity pattern. We discuss the similarities in the structural dynamics of 4PMO and 2‐thiopyrimidone (2TPM), and the results were used to correlate to the intramolecular hydrogen‐atom‐transfer process as observed by matrix‐isolation IR experiments for 4PMO. A variety of NH/CH bend modes + C = O stretch mode mark the hydrogen‐detachment‐attachment or ESIPT reaction initiated in Franck–Condon region for 4PMO and 2TPM. Copyright © 2013 John Wiley & Sons, Ltd.     

Vibronic coupling and excited‐state reaction dynamics of pyrazine in 1 1B2u (1ππ*) state by resonance Raman spectroscopy and CASSCF calculation

The photophysics and photochemistry of pyrazine (C₄H₄N₂, D_2h) after excitation to the S₂ (1 ¹B_2u, ¹ππ*) electronic state were studied by using the resonance Raman spectroscopy and complete active space self‐consistent field method calculations. The B‐band resonance Raman spectra in cyclohexane solvent were obtained at 266.0, 252.7, and 245.9 nm excitation wavelengths to probe the structural dynamics of pyrazine in the S₂ (1 ¹B_2u, ¹ππ*) state. Three electronic states 1 ¹B_3u, 1 ¹B_1g, and 1 ¹B_2g were found to couple with the S₂ (1 ¹B_2u, ¹ππ*) state. Two conical intersection (CI) points CI[S₂(B_2u)/S₁(B_3u)] and CI[S₁/S₀] and one transition state of the isomerization between pyrazine and pyrimidine were predicted to play important roles in the photochemistry of pyrazine. On the basis of the calculations, the mechanism of the photoisomerization reaction between pyrazine and pyrimidine has been proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural dynamics of 4‐cyanobenzaldehyde in S2(ππ*) state

The excited state structural dynamics of 4‐cyanobenzaldehyde (p‐CNB) were studied by using the resonance Raman spectroscopy and the quantum mechanical calculations. The experimental A‐ and B‐band absorptions were, respectively, assigned to the major n_O → π₃* and π₂ → π₃* transitions according to the B3LYP‐TD/6‐31G(d) and CIS/6‐31G(d) computations, and the resonance Raman spectra. It was determined that the actual S₂(π₂π₃) state was in energy lower than S₃(π₁π₃), which was just opposite to the B3LYP‐TD/6‐31G(d) calculated order of the S₂(π₁π₃) and S₃(π₂π₃). The vibrational assignments were carried out for the A‐ and B‐band resonance Raman spectra. The B‐band resonance Raman intensities of p‐CNB were dominated by the C2–C3/C5–C6 symmetric stretch mode ν₈, the overtones nν₈ and their combination bands with the ring C–H bend mode ν₁₇, the C9–N10 stretch mode ν₆, the C7–O8 stretch mode ν₇ and the remaining modes. The conical intersection between S₁(n_Oπ₃) and S₂(π₂π₃) states of p‐CNB was determined at complete active space self‐consistent field (CASSCF)(8,7)/6‐311G(d,p) level of theory. The B‐band short‐time structural dynamics and the corresponding decay dynamics of p‐CNB were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. The resonance Raman spectra indicated that CI[S₁(n_Oπ₃)/S₂(π₁π₂π₃π₄)] located nearby the Franck–Condon region. The excited state decay dynamics evolving from the S_{2, FC}(π₂π₃) to the S₁(n_Oπ₃) state was proposed. Copyright © 2013 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.     

A‐band structural dynamics of thioanisole by resonance Raman spectroscopy

The structural dynamics of thioanisole in the S₂(ππ*) electronic state that has large oscillator strength was studied by using the resonance Raman spectroscopy. The vibrational assignments were done for thioanisole on the basis of the FT‐Raman and FT‐IR measurements, the density‐functional theory computations and the normal mode analysis. The A‐ and B‐band resonance Raman spectra were obtained in cyclohexane, methanol and acetonitrile, in which ten modes in A’ irreducible representations were observed. The structural dynamics were obtained according to the resonance Raman intensity pattern. The vibroinc‐coupling between the S₃(πσ*) electronic state that has no oscillator strength and the S₂(ππ*) electronic state were revealed. We discuss the correlation between our present structural dynamics and the previous S₂(ππ*)/S₃(πσ*) conical intersectional dynamics revealed by resonant‐enhanced two‐photon ionization and the photofragment excitation spectroscopic study. Copyright © 2012 John Wiley & Sons, Ltd.     

Short‐time photodecay dynamics of meso‐tetra(p‐hydroxyphenyl)porphine in the condensed phase explored via resonance Raman spectroscopy and density functional theory calculation

Resonance Raman (RR) spectra of free‐base meso‐tetra(p‐hydroxyphenyl)porphine(THPP) were obtained with 397.9, 416 and 514 nm excitation wavelengths, and density functional calculations were carried out to help the elucidation of the photorelaxation dynamics of Soret (B_x and B_y bands) electronic transitions and the RR spectra of THPP. The RR spectrum indicates that the Franck–Condon (FC) region photorelaxation dynamics for the S₀ → S₅ excited electronic state is predominantly along the totally symmetric C_m phC stretching and the C_βC_β stretchingand simultaneously along the asymmetric (C_mC_α)as stretching, ν(phC  C)asstretching, δ(NH)s and γ(C_βH) vibrational relaxation processes, while that for S₀ → S₄ electronic state is predominantly along the C_m phC stretching and pyrrole breathing. The excited‐state structural dynamics of THPP determined from the RR spectra shows that internal conversion (IC) B_y → B_x electronic relaxation occurs in tens of femtoseconds, and the short‐time dynamics is interpreted using the time‐dependent wave packet theory and Herzberg–Teller (vibronic coupling) contributions. Copyright © 2010 John Wiley & Sons, Ltd.     

The excited state dynamics study of di‐2‐pyridylketone in the A‐band and B‐band absorptions by using resonance Raman spectroscopy,IR and UV–visible spectroscopy

Excitation wavelengths of 282.4, 273.9 (A band), 252.7, 239.5 and 228.7 nm (B band) resonance Raman spectra were acquired for di‐2‐pyridylketone, and density functional calculations were carried out to help in the elucidation of the photo relaxation dynamics of A‐band and B‐band electronic transitions. The resonance Raman spectra show that the intensity pattern of the A band presents great difference from that of the B band, which indicate that the short‐time A‐band (S₀→S₄) photo relaxation dynamics have substantial difference from that of B band (S₀→S₁₀) . The overall picture of short‐time dynamics and the vibronic coupling mechanisms are interpreted using Albrecht's theory. Copyright © 2012 John Wiley & Sons, Ltd.     

Structure and vibrational analysis of 1‐hydroxy naphthalene based on density functional theory calculations

The solid phase mid‐FTIR and FT‐Raman spectra of 1‐hydroxy naphthalene (HNP) were recorded in the regions 4000–400 and 4000–50 cm, respectively. The spectra were interpreted with the help of normal coordinate analysis following full structure optimization and force field calculations based on the density functional theory (DFT) using the standard B3LYP/6‐31G** method and basis set combination. The results of the calculations were applied to simulate infrared and Raman spectra of the title compound which showed excellent agreement with the observed spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational dynamics and structural investigation of 4‐benzoylpyridine

The polarized Raman spectra in different environments along with the IR counterpart of 4‐benzoylpyridine (4‐BOP) were critically analyzed to assign all of its normal modes of vibration. The knowledge of the positions of different excited electronic states (EESs)was obtained from the study of electronic absorption spectra. Measurement of Raman excitation profiles (REPs)of several normal modes was carried out to get insight into structural and symmetry properties of the molecule. All the experimental observations were substantiated and corroborated theoretically by quantum chemical calculations (QCCs). The possibility of exciton splitting of the ¹L_a band has been explored both from theoretical and experimental points of view. Copyright © 2010 John Wiley & Sons, Ltd.     

Analysis of vibrational spectra of 2‐fluoro‐6‐nitrotoluene based on density functional theory calculations

The conformational behavior and structural stability of 2‐fluoro‐6‐nitrotoluene (FNT) were investigated by utilizing density functional theory (DFT) with the standard B3LYP/6‐311 + G** method and basis set combinations. The vibrational wavenumbers of FNT were computed at DFT levels and complete vibrational assignments were made on the basis of normal coordinate calculations. Normal coordinate analysis (NCA) has been carried out to support the vibrational analysis. The results were compared with the experimental values. The observed Fourier transform infrared (FTIR) and Fourier transform (FT) Raman vibrational wavenumbers were analyzed and compared with the theoretically predicted vibrational spectra. The results of vibrational spectra of FNT were also compared with the vibrational spectra of some toluene derivatives. The assignments of bands to various normal modes of the molecules were also carried out. Copyright © 2008 John Wiley & Sons, Ltd.     

Time‐resolved spectroscopic and density functional theory investigation of the photochemistry of suprofen

The photochemistry of suprofen (SPF) was investigated by femtosecond transient absorption (fs‐TA), resonance Raman (RR) and nanosecond time‐resolved resonance Raman (ns‐TR³) spectroscopic methods to gain additional information so as to better elucidate the possible photochemical reaction mechanism of suprofen in several different solvents. In neat acetonitrile (MeCN), the fs‐TA and ns‐TR³ experimental data indicated that the lowest lying excited singlet state S₁ (nπ*) underwent an efficient intersystem crossing process (ISC) to the excited triplet state T₃ (ππ*), followed by an internal conversion (IC) process to T₁ (ππ*). In the aqueous solution, a triplet biradical species (³ETK‐1) was obtained as the product of a decarboxylation process from triplet suprofen anion (³SPF⁻) and the reaction rate of the decarboxylation process was determined by the concentration of H₂O. A protonation process for ³ETK‐1 leads to formation of a neutral species (³ETK‐3) that was directly observed by ns‐TR³ spectra, then this ³ETK‐3 species decayed via ISC process to generate final product. Copyright © 2014 John Wiley & Sons, Ltd.     

A combined experimental and density functional study of 1‐(arylsulfonyl)‐2‐R‐4‐chloro‐2‐butenes reactivity towards the allylic chlorine

Nucleophilic substitution and dehydrochlorination reactions of a number of the ring‐substituted 1‐(arylsulfonyl)‐2‐R‐4‐chloro‐2‐butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general rapidity, cheapness, and simplicity providing moderate to high yields of 1‐arylsulfonyl 1,3‐butadienes (48–95%), 1‐(arylsulfonyl)‐2‐R‐4‐(N,N‐dialkylamino)‐2‐butenes (31–53%), 1‐(arylsulfonyl)‐2‐R‐2‐buten‐4‐ols (37–61%), and bis[4‐(arylsulfonyl)‐3‐R‐but‐2‐enyl]sulfides (40–70%). The density functional theory B3LYP/6‐311++G(2d,2p) calculations of the intermediate allylic cations in acetone revealed their high stability occurring from a resonance stabilization and hyperconjugation by the SO₂Ar group. The reactivity parameters estimated at the bond critical points of the diene/allylic moiety display a high correlation (R² > 0.97) with the Hammett (σ_p) constants. 1‐Arylsulfonyl 1,3‐butadienes are characterized by a partly broken π conjugated system, which follows from analysis of the two‐centered delocalization (δ) and localization (λ) index values. The highest occupied molecular orbital energies of 1‐arylsulfonyl 1,3‐butadienes are lower than those of 1,3‐butadiene explaining their low reactivity towards the Diels–Alder condensation. Copyright © 2015 John Wiley & Sons, Ltd.     

Photofragmentation mechanisms of nickel methyl xanthate—resonance Raman and density functional theory investigation

The C‐, D‐, and E‐band resonance Raman spectra were obtained for nickel methyl xanthate (NMX) in acetonitrile solution. Density functional calculations were carried out to help elucidate its ultraviolet electronic transitions and vibrational assignments of the resonance Raman spectra associated with the C‐, D‐, and E‐band absorptions. The Franck–Condon region photodissociation dynamics of NMX in C, D, and E‐band absorptions were revealed to have multidimensional characters and to be significantly different from one another in terms of the resonance Raman intensity patterns. The photofragmentation mechanism associated with C‐, D‐, and E‐band absorptions are briefly discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Density functional theory and time‐dependent density functional theory study on a series of iridium complexes with tetraphenylimidodiphosphinate ligand

A series of heteroleptic cyclometalated Ir(III) complexes for organic light‐emitting diodes (OLEDs) application have been investigated theoretically to explore their electronic structures and spectroscopic properties. The geometries, the electronic structures, the lowest‐lying singlet absorptions and triplet emissions of Ir(dfppy)₂(tpip), Ir(tfmppy)₂(tpip), and theoretically designed models of Ir(ppy)₂(tpip) were investigated with the density functional theory (DFT)‐based approaches, where ppy = 2‐phenylpyridine, dfppy = 4,6‐difluorophenylpyridine, tfmppy = 4‐trifluoromethylphenylpyridine, and tpip = tetraphenylimidodiphosphinate. Their structures in the ground and their excited states have been optimized at the DFT/Becke 3‐parameter Lee Yang Parr (B3LYP)/Los Alamos National Laboratory 2‐double‐z (LANL2DZ) and time‐dependent DFT/B3LYP/LANL2DZ levels, and the lowest absorptions and emissions were evaluated at B3LYP and M062X level of theory, respectively. Furthermore, the energy transfer mechanism together with the advantage of low efficiency roll‐off for these complexes also can be analyzed here. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

Time‐dependent density functional theory study on the excited‐state hydrogen bonding strengthening of photoexcited 4‐amino‐1,8‐naphthalimide in hydrogen‐donating solvents

The time‐dependent density functional theory (TDDFT) method was performed to investigate the excited‐state hydrogen bonding dynamics of 4‐amino‐1,8‐naphthalimide (4ANI) as hydrogen bond acceptor in hydrogen donating methanol (MeOH) solvent. The ground‐state geometry optimizations, electronic transition energies and corresponding oscillation strengths of the low‐lying electronically excited states for the isolated 4ANi and hydrogen‐bonded 4ANi‐(MeOH)_1,4 complexes were calculated by the DFT and TDDFT methods, respectively. We demonstrated that the intermolecular hydrogen bond C═O···H–O and N–H···O–H in the hydrogen‐bonded 4ANi‐(MeOH)_1,4 is strengthened in the electronically excited state, because the electronic excitation energies of the hydrogen‐bonded complex are correspondingly decreased compared with that of the isolated 4ANi. The calculated results are consistent with the mechanism of the hydrogen bond strengthening in the electronically excited state, while contrast with mechanism of hydrogen bond cleavage. Furthermore, we believe that the transient hydrogen bond strengthening behavior in electronically excited state of fluorescent dye in hydrogen‐donating solvents exists in many other systems in solution. Copyright © 2013 John Wiley & Sons, Ltd.