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1.
Rishikesh Pandey Nagappan Rajkumar Siva Umapathy 《Journal of Raman spectroscopy : JRS》2013,44(2):270-276
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. 相似文献
2.
Wen Li Jiadan Xue Shun Cheung Cheng Yong Du David Lee Phillips 《Journal of Raman spectroscopy : JRS》2012,43(6):774-780
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. 相似文献
3.
Zhangzhu Wu Jun Xu Junmin Wan Xuming Zheng Huigang Wang Yao Tan 《Journal of Raman spectroscopy : JRS》2011,42(4):749-757
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 (Bx and By 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 Cm phC stretching and the CβCβ stretchingand simultaneously along the asymmetric (CmCα)as stretching, ν(phC C)asstretching, δ(NH)s and γ(CβH) vibrational relaxation processes, while that for S0 → S4 electronic state is predominantly along the Cm phC stretching and pyrrole breathing. The excited‐state structural dynamics of THPP determined from the RR spectra shows that internal conversion (IC) By → Bx 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. 相似文献
4.
The vibronic coupling between the first excited S1 (21Ag) and the second excited S2 (11Bu) singlet electronic states in spectroscopy of trans‐1,3,5‐hexatriene molecule is investigated on the basis of a model consisting of two electronic states coupled by two vibrational modes. Employing a perturbation theory that treats the intramolecular couplings in a perturbative manner, the absorption and resonance Raman cross sections and excitation profiles of this molecule are calculated using the time‐correlation function formalism. The non‐Condon corrections are included in evaluation of cross sections. The multidimensional time‐domain integrals that arise in these calculations have been evaluated for the case in which S0 (11Ag) S2 (11Bu) electronic transition takes place between displaced and distorted harmonic potential energy surfaces. The calculated spectra are in good agreement with the experimental ones. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
5.
LiBo Wang Wenfei Zhang Shaosong Shen Huigang Wang Xuming Zheng Anmin Zheng Yueying Chu 《Journal of Raman spectroscopy : JRS》2012,43(10):1465-1471
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. 相似文献
6.
Huigang Wang Bo Liu Yanying Zhao Xuming Zheng 《Journal of Raman spectroscopy : JRS》2009,40(9):1312-1318
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 CS stretch υ11, while the S4 state one has motions mainly via the S C S symmetric stretch υ18, CS 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. 相似文献
7.
Isabel Rozas Goar Sánchez‐Sanz Ibon Alkorta José Elguero 《Journal of Physical Organic Chemistry》2013,26(5):378-385
We have calculated the complexes formed by guanidine/guanidinium and HCl/Cl?, HNO3/NO3? and H2SO4/HSO4? both in the gas and aqueous Polarizable Continuum Model (PCM) phase to understand the effect that solvation has on their interaction energies. In the gas phase, the cation–anion complexes are much more stable than the rest; however, when PCM‐water is considered, this energetic difference is not as large due to the extra stabilization that the ions suffer when in aqueous solution. All the complexes were analyzed in terms of their AIM and NBO properties. In all cases, water solvation seems to “dampen” those properties observed in the gas phase. The values of Nucleus Independent Chemical Shift (NICS)(1) and NICS(2) indicate a huge influence of the proximity of the carbon atom for short distances; thus, the 3D NICS values on the van der Waal isosurfaces have been used to evaluate the possible Y‐aromaticity of the guanidinium system. The isosurface in this system is more similar to cyclohexane than to benzene as indication of poor aromaticity. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
8.
M. Makowski P. Zazakowny M. T. Pawlikowski 《Journal of Raman spectroscopy : JRS》2013,44(11):1548-1556
The absorption, pre‐resonance, and resonance Raman spectra of 1,4,5,8‐naphthalenetetracarboxy dianhydride (NTCDA) molecule are examined in terms of time‐dependent density functional theory at TD‐B3LYP/aug‐cc‐pVDZ and TD‐SVWN/aug‐cc‐pVDZ levels. The Franck–Condon analysis performed for two 11Ag → 11B2u and 11Ag → 11B3u overlapping transitions leads to an excellent agreement between the theoretical predictions and experimental data providing that the calculated absorption is confronted with that measured in chloroform or acetonitrile but not in the ethanol (methanol) solution. We argue that absorption spectra measured in ethanol solution already known in literature do not characterize NTCDA molecule. On the basis of the absorption and resonance scattering spectra, we may deliberate that the dimerization of NTCDA is responsible for utterly different absorption observed in ethanol (methanol) comparing with less active solvents (chloroform and acetonitrile). That conclusion is supported by the dimer vibronic theory and by the TD‐B97d computations at the aug‐cc‐pVDZ basis set level. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
9.
Ji‐Wen Jian Hai‐Bo Zhang Cong‐Qi Chen Yanying Zhao Xuming Zheng 《Journal of Raman spectroscopy : JRS》2013,44(4):582-589
The resonance Raman spectroscopy in conjunction with the density functional theory calculations were used to study the excited state structural dynamics of 2‐mercapto‐1‐methylimidazole (MMI). The experimental UV absorption bands were assigned according to the time‐dependent density functional calculations. The vibrational assignments were done for the A‐band resonance Raman spectra of MMI in water and acetonitrile on the basis of the Fourier transform infrared (FT‐IR) and FT‐Raman measurements in solid, in water and in acetonitrile and the corresponding B3LYP/6‐311+G(d, p) computations. The dynamic structures of MMI were obtained by analysis of the resonance Raman intensity pattern and normal mode analysis. The differences in the dynamic structures of MMI and thiourea were revealed and explained. The structural dynamic of MMI was found to be similar to that of 2‐thiopyrimidone in terms of major reaction coordinates and thus favored the intra‐molecular proton transfer reaction. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
10.
Huigang Wang Bo Liu Junmin Wan Jun Xu Xuming Zheng 《Journal of Raman spectroscopy : JRS》2009,40(8):992-997
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 CS stretch+ H‐CC‐H scissor υ4, accompanied by the H‐CC‐H scissor υ3, S‐C‐S symmetric stretch υ6, CC stretch υ2, and overtone of the non‐totally symmetric SC‐S2 out‐of‐plane deformation 2υ11. The excited‐state dynamics and the force constant of CS stretch calculated by the RRs were discussed. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
11.
Ming‐Xia Liu Bin‐Bin Xie Ming‐Juan Li Yan‐Ying Zhao Ke‐Mei Pei Hui‐Gang Wang Xuming Zheng 《Journal of Raman spectroscopy : JRS》2013,44(3):440-446
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. 相似文献
12.
Susmita Bhattacharya Nidhi Vyas Animesh K. Ojha Swagata Dasgupta Anushree Roy 《Journal of Raman spectroscopy : JRS》2012,43(6):718-723
The interaction of l ‐tryptophan (Trp) with silver colloids was investigated at between pH values of 6.11 and 10.6 of the sol. The measurements of surface‐enhanced Raman bands of Trp in the colloidal solution indicate the evolution of interaction between the metal particles and the molecules with increasing pH values for the sol. The experimental observations were explained using the estimated atomic charge distribution in the zwitterionic and anionic forms of the residue, obtained by density functional theory calculations. The variation in the ratio of the spectral intensities of the Fermi resonance bands with the pH reflects the effect of the colloidal environment on Trp. The results obtained can be used as a marker for describing the nature of the interaction of silver colloids with the specific terminus of the residue, at varying pH environments. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
13.
The spectra of 2,5‐dihydroxybenzoic acid (DHBA) have been recorded using Fourier transform‐infrared spectroscopy (FT‐IR) and FT‐Raman measurements. The total energy calculations of DHBA were evaluated for various possible conformers. The spectra were interpreted with the help of normal coordinate analysis based on density functional theory (DFT) using standard B3LYP/6–31G* method for the most optimized geometry. The effect of intramolecular hydrogen bonding was discussed. Normal coordinate calculations were performed with the DFT force field corrected by a recommended set of scaling factors, yielding fairly good agreement between observed and calculated frequencies. On the basis of the comparison between calculated and experimental results, assignments of fundamental modes were examined. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
14.
Time-dependent hybrid density functional theory in combination with Onsager reaction field model and super-molecular model has been applied to study solvent effects on the geometrical and electronic structures, as well as one/two-photon absorption properties, of 4-(N-(2-hydroxyethyl)-N-methyl)-amino-4'-nitroazobenzene. It is found that the short-range interaction has a large effect on the electronic structure of the solute molecule, namely, large red-shift of the maximum one-photon absorption is induced by hydrogen bonding. The solute molecule has a large two-photon absorption cross section, which is enhanced by the solvent effect. The computational results are in good agreement with measurements.[第一段] 相似文献
15.
Jian‐Li Guo Chong Liu Bin‐Bin Xie Yan‐Ying Zhao Ke‐Mei Pei Hui‐Gang Wang Xuming Zheng Yue‐Jie Ai Xue‐Bo Chen Wei‐Hai Fang Chi Shun Yeung 《Journal of Raman spectroscopy : JRS》2012,43(10):1477-1486
The photophysics and photochemistry of pyrazine (C4H4N2, D2h) after excitation to the S2 (1 1B2u, 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 1B2u, 1ππ*) state. Three electronic states 1 1B3u, 1 1B1g, and 1 1B2g were found to couple with the S2 (1 1B2u, 1ππ*) state. Two conical intersection (CI) points CI[S2(B2u)/S1(B3u)] 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. 相似文献
16.
The problem of complex Fermi resonance (FR) involving a local vibration is considered. It is shown for the first time that in the PbI2 crystal, owing to the features of phonon bands, the following two effects superpose on each other: (1) the traditional FR between the fundamental Ω(A1g) vibration and the two‐phonon states (TPS) arising from the 2Ω(Eu) vibrations, and (2) the FR between the impurity vibration and the same TPS band. It is shown theoretically that in the case of such complex FR the shape of the spectrum strongly depends on the impurity concentration, anharmonic constants and the phonon band structure. An analysis of experimental data and comparison with theory is made. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
17.
Yong Du Jiadan Xue Chensheng Ma Wai Ming Kwok David Lee Phillips 《Journal of Raman spectroscopy : JRS》2008,39(4):503-514
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. 相似文献
18.
Excited‐state hydrogen bond strengthening of coumarin 153 in ethanol solvent: a TDDFT study
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Jinmei Xu Junsheng Chen Shunle Dong Aiping Fu Hongliang Li Tianshu Chu 《Journal of Physical Organic Chemistry》2016,29(6):305-311
So far, coumarin dyes have been extensively studied with various means to understand their photophysical behaviors and photochemical properties. Here, our performing time‐dependent density functional theory calculation is aimed at exploring the excited‐state hydrogen bonding dynamics of coumarin 153 (C153) in protic ethanol (EtOH) solvent. The calculated results suggest that the excited‐state hydrogen bond C?O?H?O between C?O group and O?H group in the C153‐EtOH complex is strengthened, and the S0 → S1 transition of the complex corresponds to the highest occupied molecular orbital (HOMO) hopping to the lowest unoccupied molecular orbital (LUMO). The excited‐state hydrogen bond strengthening has been further confirmed by its larger binding energy in the S1 state than in the S0 state. In addition, because of the formation of the hydrogen bond C?O?H?O, a red shift of about 7 nm occurs in the electronic spectra of the C153‐EtOH complex, which is in good accordance with the experiment result. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
19.
The effect of anti-hydrogen bond on Fermi resonance: A Raman spectroscopic study of the Fermi doublet ν1—ν12 of liquid pyridine
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The effects of anti-hydrogen bond on the ν1—ν12 Fermi resonance (FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of Fermi coupling coefficient W of the ring breathing mode ν 1 and triangle mode ν 12 of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the ν1—ν12 Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν1—ν12 FR of pyridine. According to the mechanism of the formation of anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν1—ν12 FR of pyridine is given. 相似文献
20.
Ben‐Feng He Yan‐Ying Zhao Ke‐Mei Pei Hui‐Gang Wang Xu‐Ming Zheng 《Journal of Raman spectroscopy : JRS》2013,44(6):834-840
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 πH→π*L and πH→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. 相似文献