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The dinoflagellate cysts present in the ballast water sediment of foreign ships in Shanghai Port have not been previously studied. Therefore, sediment samples were collected from the ballast water of 16 foreign ships in Shanghai Port, and the types of dinoflagellate cysts were identified and their abundance was calculated, with a specific focus on the analysis of toxic and harmful dinoflagellates. Moreover, simulations of temperature and salinity conditions throughout the year in the Shanghai port waters were conducted to carry out dinoflagellate cyst germination experiments, with analyze and compare the germinated dinoflagellate cysts under different conditions. Dinoflagellate cysts were found in 100 % of the ship sediment samples, including a total of 9 species of toxic and harmful dinoflagellate cysts. In the germination experiment, 15 °C was found to be the optimal temperature for the germination of dinoflagellate cysts in ballast water sediment, and high salinity is more favorable for cyst germination., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Nitro-polycyclic aromatic hydrocarbons (nitro-PAHs), often found in polluted air, are carcinogenic and mutagenic. The nitro group increases the spin-orbit coupling and results in the lowest excited triplet (T 1 ) on the picosecond time scale with a high yield. The electron-donating substituents have a significant influence on the photophysics and photochemistry of nitro-PAHs. We used transient absorption spectroscopy and kinetic analysis to investigate the reactivities of the T 1 state 1-methoxy-4-nitronaphthalene ( 3 MeO-NN) and 1-methyl-4-nitronaphthalene ( 3 Me-NN). The results show that the methoxy and methyl substitutions have a minor effect on their hydrogen abstraction and electron accepting abilities. The main distinction is their reaction rates towards protons. The second order rate constant of 3 MeO-NN towards protons is three orders of magnitude greater than that of 3 Me-NN, indicating that 3 MeO-NN has a stronger hydrogen bond accepting ability. The kinetic analysis reveals that the dimer of 2,2,2-trifluoroethanol participates in the reaction with 3 MeO-NN. These results suggest that the formation of the hydrogen-bonded complex is responsible for the unusually short lifetime of 3 MeO-NN in methanol solution and the lack of hydrogen abstraction radicals during the decay of 3 MeO-NN in methanol., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

8-Hydroxy-5-nitroquinoline (NO 2 -QN-OH) is an antimicrobial, anti-inflammatory and anticancer agent, and has been approved for use in the treatment of diseases. Its photosensitivity, however, cannot be overlooked. The photochemistry of 8-hydroxy-5-nitroquinoline in acetonitrile is investigated using transient absorption and time-resolved resonance Raman spectroscopies. By identifying the short-lived intermediates during the photoreaction, it is clear that the T n state NO 2 -QN-OH is generated in 0.8 ps via an ultrafast ISC, followed by the IC in 8.5 ps to produce the T 1 state. In neat acetonitrile, the T 1 state NO 2 -QN-OH undergoes intramolecular proton transfer and tautomerizes to form T 1 state NO 2 -QNH-O. To our knowledge, this is the first time that the intramolecular excited state proton transfer of hydroxyl-quinolines in an aprotic polar solvent is observed.

Hydroxyaromatic compounds (ArOHs) have a wide range of applications in catalytic synthesis and biological processes due to their increased acidity upon photo-excitation. The proton transfer of ArOHs via the excited singlet state has been extensively studied. However, there has still been a debate on the unique type of ArOH that can undergo an ultrafast intersystem crossing. The nitro group in p -nitrophenylphenol (NO 2 -Bp-OH) enhances the spin-orbit coupling between excited singlet states and the triplet manifold, enabling ultrafast intersystem crossing and the formation of the long-lived lowest excited triplet state (T 1 ) with a high yield. In this work, we used time-resolved transient absorption to investigate the excited state proton transfer of NO 2 -Bp-OH in its T 1 state to t -butylamine, methanol, and ethanol. The T 1 state of the deprotonated form NO 2 -Bp-O - was first observed and identified in the case of t -butylamine. Kinetic analysis demonstrates that the formation of the hydrogen-bonded complex with methanol and ethanol as proton acceptors involves their trimers. The alcohol oligomer size required in the excited state proton transfer process is dependent on the excited acidity of photoacid.

Photophysical and photochemical reactions of microsolvation clusters are attracting an increasing attention due to their wide applications in materials science and biology. In this paper, 1, 2, 4-triazole-3-thione (3TT) is investigated in solid, protic, and aprotic solvents using FT-Raman, resonance Raman and electronic absorption spectroscopic experiments. The structures of microsolvation clusters in solvents were confirmed by 488 nm Raman spectroscopy combining with density functional theory (DFT) calculation. Steady-state absorption and resonance Raman spectra of 3TT in different environments indicate that the intermolecular hydrogen bonding may reveal important insights in the photophysical and photochemical process. With the aid of DFT and time-dependent density functional theory (TDDFT) calculations, we assigned the observed Raman spectra to the microsolvation clusters in acetonitrile, water and methanol, and carried out preliminary investigations on spectrum shifts of UV and Raman spectra due to the hydrogen bonding with the solvent molecules. The intermolecular >NH···O and >=S···H hydrogen bonding interactions, which are the key constituents of stable thione structure of 3TT, revealed the obvious spectrum shifts of 3TT, including Raman and absorption shifts in CH 3 CN, CH 3 OH and H 2 O. The hydrogen bond sites were further confirmed to be located on the functional group SCNH of 3TT with CH 3 CN, H 2 O and CH 3 OH., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The vibrational frequency shift in the C=O stretch mode of 2-thiophenecarboxaldehyde (2TC) in the condensed phase is still not fully understood. In this paper, the vibrational spectra of 2TC were investigated using the FT-Raman, FT-IR and resonance Raman spectroscopies in conjunction with the density functional theory calculation. The pure compound (in the neat liquid) exhibits three vibrational bands 1658, 1672 and 1687 cm -1 in the ν C=O spectral region. It differs from the band pair 1672 and 1682 cm -1 for 2-cyclohexene-1-one (CHO) and the single band 1700 cm -1 for benzaldehyde. The relative intensities of observed bands vary with the polarity of aprotic solvents and the compound's concentration. In a diluted solution, the strongest band in the resonance Raman spectra of 2TC appears the C=O stretch mode at 1690 cm -1 in cyclohexane and 1674/1675 cm -1 in acetonitrile. The imparting factors that shift the C=O stretch mode frequency in the neat liquid and solvents with different polarities were examined. The spectral sources of the vibrational bands at 1658 and 1672 cm -1 in the neat liquid and a dilute solution were determined, and the resonance Raman spectra were assigned. It is concluded that tetramers and monomer are the major sources of the bands at 1658 and 1672 cm -1 in the neat liquid, respectively, while the monomer is the main source of the bands at 1674/1675 cm -1 in acetonitrile and the band at 1690 cm -1 in cyclohexane with a dilute concentration. The band's source at 1662/1663 cm -1 in acetonitrile (a dilute concentration) can be either the dimers or 2TC-CH 3 CN clusters. The C=O bond's electronic charge density is the main factor that shifts the vibrational frequency of the C=O stretch mode of 2TC monomer when an aprotic solvent is used. The larger the polarity of an aprotic solvent, the more negative the electronic charge-density of the C=O bond for the monomer, the lower the frequency of the C=O stretch mode., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This article aims to correlate the noncoincidence effect phenomenon with the aggregation state of acetylacetone C[double bond, length as m-dash]O stretching in a binary mixture. C[double bond, length as m-dash]O stretching noncoincidence effect (NCE) was observed not only between IR and Raman spectra but also between the isotropic and anisotropic Raman spectra of acetonylacetone. The difference in C[double bond, length as m-dash]O stretching wavenumbers of the isotropic and anisotropic Raman spectra (NCE value) in a binary mixture at different concentrations has been calculated. We found that both isotropic and anisotropic Raman wavenumbers of C[double bond, length as m-dash]O stretching increase with the dilution of acetonylacetone by CCl 4 while the NCE value decreases. These noncoincidence and concentration effect phenomena seem to go against the quantum theory. Herein, we proposed an aggregation-induced split (AIS) model to explain the NCE phenomenon and concentration effect. The experimental data were consistent with the DFT calculations performed at the B3LYP-D3/6-311++G (d,p) levels based on the proposed model. The dynamics of transformation from monomers to an aggregated structure can be easily controlled by tuning the concentration. Solvent dependent experiments show that the value of NCE decreased with the increase of the solvent dielectric constant at the same concentration, which is in accordance with Logan's theory., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

The excited state decay process of N-heterocyclic compounds is attracting increasing attention due to their fundamental applications in pharmaceutical and biological sciences. In this study, 3-amino-5-mercapto-1,2,4-triazole (AMT) was investigated in solid, protic, and aprotic solvents using vibrational and electronic spectroscopies combined with density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The steady absorption and resonance Raman spectra indicated that the AMT structure was quite sensitive to the polarity and proton of the solvent, and the pH environments. The intermolecular hydrogen bonding may contribute significantly to the decay channels of the singlet excited S 2 (ππ*) state process. Moreover, ns-transient absorption spectroscopy detected the short-time triplet species with ∼200 ns lifetime in solvents. The DFT and TDDFT calculations interpreted the photophysical and photochemical process from the excited S 2 (ππ*) state, including the singlet and triplet decay mechanisms., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Microsolvation effects on the excited state deactivation dynamics of 2-thiocytosine (2tC) were studied in hydrogen-bonded 2tC clusters with protic solvents using resonance Raman, FT-IR, FT-Raman, UV-vis spectroscopy combining with density functional theoretical calculation. Two protic solvents, water (H 2 O) and methanol (MeOH), and one aprotic solvent, acetonitrile (MeCN), were used to investigate the 2tC(H 2 O) 1 - 5 , 2tC(MeOH) 1 - 5 , and 2tC(MeCN) 1 - 3 microsolvated clusters. In CH 3 OH and H 2 O solvents, most of the Raman shifts were due to the vibration modes of 2tC(solvent) n (solvent = H 2 O, CH 3 OH; n = 1-4) clusters via intermolecular NH⋯O hydrogen bonds (HB). The intermolecular >NH⋯O hydrogen bond interactions, which are the key constituents of stable thione structure of 2tC, revealed the spectra difference of 2tC in CH 3 CN, CH 3 OH and H 2 O. With the aid of electronic structural and vibration frequency calculations, the observed Raman spectra were assigned to the low energy isomers of 2tC(solvent) 2 (solvent = H 2 O, CH 3 OH) clusters in water and methanol and 2tC(CH 3 CN) in acetonitrile solvents. 2tC(solvent) 2 clusters in water and methanol may prohibit or promote excited state proton transfer reaction from sulfur atom to neighbor nitrogen atom due to the hydrogen bonding chain between 2tC and protic solvent molecules. Our experimental and theoretical studies confirmed that the hydrogen bond sites were located on the specified functional group SCNH of 2tC with solvent molecules., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

The initial nonadiabatic decay dynamics of E,E-2,4-hexadienal (HAL) in the light absorbing S 2 (ππ * ) state were studied using resonance Raman spectroscopy and complete-active space self-consistent field (CASSCF) calculations. The UV and vibrational spectra were assigned on the basis of the UV absorption, Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-band resonance Raman spectra in cyclohexane and acetonitrile were obtained at 282.4, 273.9, 266.0, 252.7, and 245.9 nm excitation wavelengths, respectively, to probe the corresponding structural dynamics of HAL. The A-band absorption cross section and the corresponding absolute resonance Raman cross sections were simulated using a simple model based on the time-dependent wave-packet theory in a Brownian oscillator model. The geometric structures of the singlet electronic excited states and their curve-crossing points were optimized at the CASSCF level of theory. The obtained short-time structural dynamics in easy-to-visualize internal coordinates were then compared with the CASSCF-predicted structural-parameter changes of S 2 (ππ * )S 1 (nπ * )-n (n = 1-4). Our results indicate that the initial population of HAL in the S 2 state ramifies in or nearby the Franck-Condon (FC) region, leading to five S 2 (ππ * ) → S 1 (nπ * ) internal conversion pathways due to the flexibility of the molecular chain and the different electronic resonant structures formed nearby FC of the S 2 state. Then, the formed S 1 transient species, which have different geometric structures and different energy partitions, undergo different photophysical processes, such as S 1 → S 0 internal conversion, S 1 → T 1 intersystem crossing, and the S 1 → S' 1 photoisomerization reaction. The substitution effect on the S 2 (ππ * ) → S 1 (nπ * ) internal conversion dynamics and the trans-cis photoisomerization reaction is proposed in terms of the p-π conjugation interaction or the p-σ superconjugation interaction.

The components of isotropic Raman and anisotropic Raman for dimethyl carbonate (DMC) dispersed in cyclohexane and acetone at different volume fractions were recorded separately. The noncoincidence effects (NCE) of the ν 7 (C=O) stretching mode were calculated accordingly. The NCE values (Δν NCE ) of the ν 7 (C=O) versus DMC volume fractions in the DMC/C 6 H 12 mixtures exhibits a convex (upward) curvature pattern, while the Δν NCE vs concentration in the DMC/CH 3 COCH 3 mixtures exhibits a concave (downward) curvature. These different NCE behaviors in the different binary mixtures may arise from the solvent-induced aggregation character. Thus, monomer and dimer structures of DMC were optimized and the vibration spectra were obtained using density functional theory (DFT) calculations. An aggregation model was suggested to expound the DMC's characteristic NCE behavior and concentration effect. We found that the theoretical spectra from DFT/polarizable continuum model calculation based on the aggregation model is in accordance with our experimental data. Solvent-dependent experiments show the Δν NCE values increase with the decrease of the solvent dielectric constant under the identical volume fractions., Competing Interests: The authors declare no competing financial interest.

Intramolecular charge transfer (ICT) is an important photochemical process. In contrast to those in singlet manifold, triplet ICT states were less studied. In this paper, the lowest excited triplet state (T 1 ) of 4‑amino‑4'‑nitrobiphenyl (NH 2 -Bp-NO 2 ) was recorded with nanosecond transient absorption spectroscopy in acidic acetonitrile and alcoholic solutions. By employing the Kamlet-Taft model to analyze the correlation between absorption maxima and alcohol solvent properties including polarity/polarizability, abilities of hydrogen bond donating and hydrogen bond accepting, hydrogen bond configuration in the ground state (S 0 ) and T 1 was resolved. The results suggest that the hydrogen bond between amino H and alcohol is dominant in S 0 , while in T 1 , hydrogen bonds between amino H and alcohol, between nitro O and alcohol have comparable contribution. By examination of the 1‑naphthol quench effect on T 1 , the hydrogen bond between nitro O and alcohol was confirmed present. Theoretical calculation results on the model of NH 2 -Bp-NO 2 -(MeOH) 3 also indicate that hydrogen bonds between amino H and alcohol, between nitro O and alcohol are both much stronger in T 1 than in S 0 . In acidic acetonitrile solution, in S 0 of NH 2 -Bp-NO 2 the amino group is protonated with pK a of 4.5, meanwhile in T 1 the nitro group is much easier to be protonated than in S 0 . Its conjugated acid was measured to have a pK a of 3.1., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Hydrogen bonding is a weak chemical interaction widely existed in the variety of organic and biological molecules. As an important structural motif of pyrimidine bases, the solvent effect of the hydrogen bonding of 2-cyclohexen-1-one (CHO) and 3-methyl- 2-cyclohexen-1-one (3MCHO) and its effect on the frequency shift of the CO stretching mode were investigated by using the FT-Raman and UV absorption spectra and density functional theory calculations. The electronic transitions associated with the UV absorptions in different solvents were calculated at B3LYP-TD/6-31++G(d,p) level of theory and employing SCIPCM solvent model. The vibrational spectra of CHO and 3MCHO were assigned on the basis of the FT-Raman spectra in neat liquid and different solvents, the calculated vibrational spectra of monomer and CHO dimers, and the concentration dependent experiments of the band pair intensities. Hydrogen bonding energies of CHO-(H 2 O) n (n = 1,2) clusters were predicted. The results reveal that the CHO-(H 2 O) 2 cluster and CHO monomer are respectively the major source of spectral observation in water and cyclohexane, while CHO dimmer and CHO monomer coexist in acetonitrile. The difference in the frequency of the ν C=O stretching mode between 3MCHO monomer and CHO monomer in cyclohexane were explored., (Copyright © 2018. Published by Elsevier B.V.)

Carbon quantum dots were successfully doped into anatase TiO 2 single crystal nanosheets (TNS) with exposed {001} and {101} reactive facets by a facile solvothermal process. SEM and TEM confirmed the as-prepared TiO 2 nanosheet structure and that the dominant exposed face is the {001} facet, and the loaded N-CDs are nearly spherical with an average size of about 3 nm. XPS results confirmed that the deposited N-CDs were chemically integrated into the TiO 2 nanosheets. UV-vis DRS spectroscopy shows that with the dotting of N-CDs, the absorption edge of N-CDs/TNS has been extended into the visible light region. The ability of the N-CDs/TNS to degrade Rhodamine B (RhB) in aqueous solution under visible light irradiation ( λ ≥ 400 nm) was investigated. The results show that the photocatalytic performance of N-CDs/TNS was substantially improved relative to pure TNS. The photodegradation efficiency reached its maximum value with 6 mL of N-CDs/TNS, showing a 9.3-fold improvement in photocatalytic activity over TNS. Fluorescence spectroscopy (PL) and electron paramagnetic resonance (EPR) studies were conducted to characterize the active species during the degradation period, based on which the possible photodegradation mechanism of N-CDs/TNS by visible light irradiation was given., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

The microsolvation and photophysics of 3-amino-1,2,4-triazole (3AT) after excitation to the light-absorbing S 2 (nπ*) state were studied by using resonance Raman spectroscopy and single component artificial force-induced reaction (SC-AFIR) in a global reaction route mapping (GRRM) strategy. The vibrational spectra were assigned on the basis of experimental data and density functional theory (DFT) calculations. The resonance Raman spectra of 3AT were measured to probe the excited state structural dynamics in the Franck-Condon region. The conformations of 3AT(CH 3 CN) 1 , 3AT(CH 3 OH) 2 , and 3AT(H 2 O) 2 clusters were determined by combining vibrational spectrum experiments and B3LYP/6-311++G(d,p) computations. DFT calculations were carried out to obtain the minimal excitation energies of the lower-lying singlet excited states, and the curve-crossing points. It was revealed that the short-time structural dynamics of 3AT were dominated by the N-N stretching coordinates. An excited state decay mechanism is proposed: 3AT is initially excited to the S 2 (nπ*) state, then the conical intersection (CI) of the S 2 (nπ*)/S 1 (ππ*) potential energy surfaces is crossed, and 3AT then decays to the lower solvent-dependent excited state S 1 (ππ*). It subsequently returns to the S 0 state, accompanied by a large Stokes fluorescence shift, which was interpreted as the stabilized S 1 (ππ*) excited state bonding to several water molecules via intermolecular hydrogen bonding.

The vibrational spectra of 4,6-dimethyl-2-mercaptopyrimidine (DMMP) in acetonitrile, methanol, and water were assigned by resonance Raman spectroscopy through a combination of Fourier-transform infrared spectroscopy (FT-IR), FT-Raman UV-vis spectroscopy, and density functional theoretical (DFT) calculations. The FT-Raman spectra show that the neat solid DMMP is formed as a dimer due to intermolecular hydrogen bonding. In methanol and water, however, the majority of the Raman spectra were assigned to the vibrational modes of DMMP(solvent) n ( n = 1-4) clusters containing NH···O hydrogen bonds. The intermolecular NH···O hydrogen bond interactions, which are key constituents of the stable DMMP thione structure, revealed significant structural differences in acetonitrile, methanol, and water. In addition, UV-induced hydrogen transfer isomeric reactions between the thione and thiol forms of DMMP were detected in water and acetonitrile. DFT calculations indicate that the observed thione → thiol tautomerization should occur easily in lower excited states in acetonitrile and water.

Solvent assisted excited state intramolecular proton or hydrogen transfer has received much attention in bi-functional molecules with hydrogen donating and hydrogen accepting groups. As a typical photoacid, 1-naphthol exhibits photo-stable behavior in methanol; whether this would be disrupted by a bonded hydrogen accepting group contained in the molecule is still not assured. We present nanosecond transient absorption measurements relating to kinetics and the characteristic absorption of key intermediates upon the excitation of 4-nitro-1-naphthol in alcoholic solutions, and also transient resonance Raman spectroscopy studies combined with theoretical calculations to identify the structures of these intermediates, and we reveal the reaction mechanism to be stepwise deprotonation, hydrogen abstraction and protonation. These results demonstrate that alcohol assisted intramolecular proton or hydrogen transfer cannot occur in this system, but that the solvent cluster plays an important role during such stepwise reactions.

Irradiation of nitro-PAHs in solution at ambient conditions leads to formation of its lowest excited triplet, dissociation intermediates nitrogen oxide (NO • ) and aryloxy radical (Ar-O • ). Experimental and theoretical studies demonstrated that Franck-Condon excited singlet state S FC (ππ*) to a receiver, higher-energy triplet state T n (nπ*) controlled the ultrafast population of the triplet state and, hence, the slight fluorescence yield of nitronaphthalenes. However, the detailed information about the curve-crossings of potential energy surfaces and the major channels for forming T 1 species and Ar-O • radical were unclear. Here, by using the CASSCF//CASPT2 method, an efficient decay channel is revealed: S 2-FC-1NN → S 2-MIN-1NN or S 2 T 3-MIN-1NN → T 3-MIN-1NN or T 3 T 2-MIN-1NN → T 2-MIN-1NN or T 2 T 1-MIN-1NN → T 1-MIN-1NN . This explains the high yield of T 1-1NN species and minor yield of Ar-O • and NO • radicals. The calculation results suggest the bifurcation processes take place predominantly after the internal conversion to the T 1-1NN state via T 2 T 1-MIN-1NN , one leads to T 1-MIN-1NN , while the other to T 1-MIN-ISO to produce Ar-O • and NO • radicals.

Nanosecond transient absorption and theoretical calculations have been used to investigate the intermolecular hydrogen abstractions from alcohols and 1-naphthol by the lowest excited triplet (T 1 ) of 1-chloro-4-nitronaphthalene upon excitation of the compound in organic solvents. The hydrogen abstraction of T 1 from hydroxy group of 1-naphthol takes place through an electron transfer followed by a proton transfer through hydrogen bonding interaction with rate constants of ∼10 9 M -1 s -1 . Hydrogen-bonding is crucial in this process, indicated by the observation of a half reduction for T 1 yield when increasing the concentration of 1-naphthol. The hydrogen abstraction in this way can be decelerated by increasing solvent polarity and hydrogen-bonding donor ability. The T 1 of 1-chloro-4-nitronaphthalene can undergo one-step H atom abstraction from alkyl hydrogen in alcoholic solvents, with rate constants of ∼10 4 M -1 s -1 , and produce radical intermediates with the absorption maximum at 368 nm. DFT calculation results indicate both oxygens of the nitro group are active sites for hydrogen abstraction, and the difference of activation barriers for formation of two radical isomers is only 1.0 kcal/mol.

In the paper, diverse tautomers of 3-amino-1,2,4-triazole (3AT) in solid and polar solvent have been explored by FT-IR, FT-Raman and 488nm Raman experiments combing with quantum chemical theoretical calculation using PCM solvent model and normal mode analysis. The vibrational spectra prefer the 3-amino-1,2,4-2H-triazole (2H-3AT) dimer in solid, while in a polar solvent 3AT is apt to the 3-amino-1,2,4-2H-triazole (2H-3AT) monomer. The significant wavenumber difference and Raman intensity patterns in solid and different solvents are induced by hydrogen bond perturbation along >NH⋯N≤ hydrogen bonds on five-membered N-heterocyclic ring. The ground state proton transfer reaction mechanism along the five-membered N-heterocyclic ring is supported by intermolecular hydrogen bonding between 3AT and protonic solvent molecules., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The isotropic and anisotropic parts Raman spectra of γ-Caprolactone in the binary mixture at different concentrations have been measured. The non-coincidence effect (NCE) of γ-Caprolactone was determined in carbon tetrachloride solution and DMSO solution. The NCE of the ν 11 (C=O) stretching mode in the γ-Caprolactone/DMSO mixtures exhibits a linear plot, in contrast to that in the γ-Caprolactone/CCl 4 mixtures, which shows an upward (convex) curvature. The reduction and enhancement of the dimer structure (short-range orientational order) of γ-Caprolactone in the γ-Caprolactone/DMSO and γ-Caprolactone/CCl 4 mixtures respectively may play a major role in shifting of peak frequencies, thus the geometries of monomer and dimer of γ-Caprolactone were calculated at the B3LYP-D3/6-311 G (d,p) level of theory. We proposed aggregated model to explain the γ-Caprolactone C=O vibration NCE phenomenon and its concentration effect and found it largely consistent with our experimental findings. Solvent dependent experiment show the value of NCE declined with the increase of the solvent dielectric constant under the same condition which is consistent with the Logan's theory.

This corrects the article DOI: 10.1038/srep43835.

The excited-state structural dynamics and the decay mechanism of 2(1H)-pyridinone (NHP) after excitation to the S 4 (2 1 ππ * ) light-absorbing state were studied using resonance Raman spectroscopy and complete-active space self-consistent field (CASSCF) calculations. The B-band absorption cross-section and the corresponding absolute resonance Raman cross-sections were simulated using a simple model based on time-dependent wave-packet theory. The geometric structures of the singlet electronic excited states and their curve-crossing points were optimized at the CASSCF level of theory. The obtained short-time structural dynamics in easy-to-visualize internal coordinates were then compared with the CASSCF-predicted structural-parameter changes of S 4 (2 1 ππ * )/S 3 (2 1 nπ * )-MIN, S 4 (2 1 ππ * )/S 1 (1 1 nπ * )-MIN, and S 4 (2 1 ππ * )-MIN. Our results indicate that the initial population of NHP in the S 4 state bifurcates in or near the Franck-Condon region, leading to two predominant (S 4 S 3 -MIN and S 4 S 1 -MIN) internal conversion pathways. The lowest-lying S 2 (1 1 ππ * ) excited state is finally formed via subsequent internal conversions S 3 (2 1 nπ * )/S 2 (1 1 ππ * )-MIN and S 1 (1 1 nπ * )/S 2 (1 1 ππ * )-MIN. The enol-keto tautomeric mechanism does not seem to play a role. The decay mechanism in the singlet realm is proposed.

The isotropic and anisotropic Raman spectra of acetone and deuterated acetone isolated in an argon matrix have been recorded for the understanding of noncoincidence effect (NCE) phenomenon. According to the matrix isolated Raman spectra and DFT calculations, we proposed aggregated model for the explanations of the acetone C=O vibration NCE phenomenon and its concentration effect. The experimental data were in consistence with the DFT calculations performed at the B3LYP-D3/6-311 G (d,p) levels based on the proposed model. The experimental identification of the monomer, dimer and trimer are reported here, and the dynamic of the transformation from monomer to aggregated structure can be easily controlled by tuning annealing temperature.

The vibration spectra of 5-(methylthio)-1,3,4-thiadiazole-2(3H)-thione (MTTN) in acetonitrile (CH 3 CN), methanol (CH 3 OH) and water (H 2 O) solvents were collected and evaluated via deuterium isotopic substitution Raman spectroscopic experiments. These experiments were combined with the quantum chemical theoretical calculations using the PCM solvent model and normal mode analysis. The results confirmed that the MTTN in CH 3 CN, CH 3 OH and H 2 O have hydrogen bonding (H-bonding) MTTN(solvent) n clusters that produce significantly different Raman intensity patterns in different solvents. Combined with the normal Raman assignment, most resonance Raman spectra were assigned to the vibration modes of the H-bonding MTTN(CH 3 CN), MTTN(CH 3 OH) 3 and MTTN(H 2 O) 3 clusters in CH 3 CN, CH 3 OH and H 2 O. The theoretically-predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands. The intermolecular>NH⋯O and >NH⋯N H-bonding interactions are key constituents of stable thione structures in MTTN. This underlines the significant structural differences of MTTN in CH 3 CN, CH 3 OH and H 2 O. H-bonding perturbation of MTTN reveal important insights about the intermolecular excited state proton transfer (ESPT) reaction mechanisms in the Franck-Condon region structural dynamics of the thione→thiol tautomer in CH 3 OH and H 2 O., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Femtosecond (fs) and nanosecond (ns) transient absorption (TA) and single pulse transient resonance Raman spectroscopic investigation of the intermediates after laser photolysis of 4-phenoxyphenyl azide in acetonitrile and mixed aqueous solution is reported. fs-TA results show that the singlet 4-phenoxyphenylnitrene was produced immediately after photolysis of the azide. Then, the singlet nitrene underwent intersystem crossing (ISC) and ring expansion to generate triplet nitrene and ketenimine in acetonitrile with t = 346 ps or protonation in mixed aqueous solution with t = 37 ps, respectively, a little slower than the counterparts of the methoxy one (108 and 5.4 ps for ISC and protonation processes, respectively). The transient Raman spectrum combined density functional theory (DFT) calculation predicting the structure and vibrational frequencies suggested that phenoxyphenylnitrenium ion has a comparable quinoidal character to that of methoxy- and ethoxy-phenylnitrenium ions. All of these results indicated that the phenoxy substitution has some impact on the reactivity of phenylnitrene but a slight influence on the structure of phenylnitrenium ion.

Ultrahigh quantum yields of intersystem crossing to the lowest triplet state T1 are observed for 2-thiouracils (2TU), which is in contrast to the natural uracils that predominantly exhibit ultrafast internal conversion to the ground state upon excitation to the singlet excited state. The intersystem crossing mechanism of 2TU has recently been investigated using second-order perturbation methods with a high-level complete-active space self-consistent field. Three competitive nonadiabatic pathways to the lowest triplet state T1 from the initially populated singlet excited state S2 were proposed. We investigate the initial decay dynamics of 2TU from the light absorbing excited states using resonance Raman spectroscopy, time-dependent wave-packet theory in the simple model, and complete-active space self-consistent field (CASSCF) and time dependent-Becke's three-parameter exchange and correlation functional with the Lee-Yang-Parr correlation functional (TD-B3LYP) calculations. The obtained short-time structural dynamics in easy-to-visualize internal coordinates were compared with the CASSCF(16,11) predicted key nonadiabatic decay routes. Our results indicate that the predominant decay pathway initiated at the Franck-Condon region is toward the S2/S1 conical intersection point and S2T3 intersystem crossing point, but not toward the S2T2 intersystem crossing point.

Intramolecular hydrogen abstraction reactions among ketoprofen (KP) and purine nucleoside dyads have been proposed to form ketyl-sugar biradical intermediates in acetonitrile. Femtosecond transient absorption studies on KP and purine nucleoside dyads reveal that the triplet state of the KP moiety of the dyads with cisoid structure decay faster (due to an intramolecular hydrogen abstraction reaction to produce a ketyl-sugar biradical intermediate) than the triplet state of the KP moiety of the dyads with transoid structure detected in acetonitrile solvent. For the cisoid 5-KP-dG dyad, the triplet state of the KP moiety decays too fast to be observed by ns-TR(3); only the ketyl-sugar biradical intermediates are detected by ns-TR(3) in acetonitrile. For the cisoid 5-KP-dA dyad, the triplet states of the KP moiety could be observed at early nanosecond delay times, and then it quickly undergoes intramolecular hydrogen abstraction to produce a ketyl-sugar biradical intermediate. For the cisoid 5-KPGly-dA and transoid 3-KP-dA dyads, the triplet state of the KP moiety had a longer lifetime due to the long distance chain between the KP moiety and the purine nucleoside (5-KPGly-dA) and the transoid structure (3-KP-dA). The experimental and computational results suggest that the ketyl-sugar biradical intermediate is generated with a higher efficiency for the cisoid dyad. However, the transoid dyad exhibits similar photochemistry behavior as the KP molecule, and no ketyl-sugar biradical intermediate was observed in the ns-TR(3) experiments for the transoid 3-KP-dA dyad.

The photophysics and photochemistry of thioacetamide (CH3CSNH2) after excitation to the S2 electronic state were investigated by using resonance Raman spectroscopy in conjunction with the complete active space self-consistent field (CASSCF) method and density functional theory (DFT) calculations. The A-band resonance Raman spectra in acetonitrile, methanol, and water were obtained at 299.1, 282.4, 266.0, 252.7, and 245.9 nm excitation wavelengths to probe the structural dynamics of thioacetamide in the S2 state. CASSCF calculations were done to determine the transition energies and structures of the lower-lying excited states, the conical intersection points CI(S2/S1) and CI(S1/S0), and intersystem crossing points. The structural dynamics of thioacetamide in the S2 state was revealed to be along eight Franck-Condon active vibrational modes ν15, ν11, ν14, ν10, ν8, ν12, ν18, and ν19, mostly in the CC/CS/CN stretches and the CNH8,9/CCH5,6,7/CCN/CCS in-plane bends as indicated by the corresponding normal mode descriptions. The S2 → S1 decay process via the S2/S1 conical intersection point as the major channel were excluded. The thione-thiol photoisomerization reaction mechanism of thioacetamide via the S2,FC → S'1,min excited state proton transfer (ESPT) reaction channel was proposed.

The photophysics of two α,β-carboxylic methyl esters after excitation to the light absorbing S2(ππ(*)) state were studied by using the resonance Raman spectroscopy and complete active space self-consistent field (CASSCF) method calculations. The vibrational spectra were assigned on the basis of the experimental measurements and the B3LYP/6-31G(d) computations, as well as the normal mode analysis. The A-band resonance Raman spectra of methyl 2,4-pentadienoate (M24PDA) and methyl trans cronoate (MTCA) were measured to probe the structural dynamics in Franck-Condon region. CASSCF calculations were done to obtain the minimal excitation energies and geometric structures of the lower-lying singlet and triplet excited states, and the curve-crossing points. It was revealed that the short-time structural dynamics of M24PDA was dominated by the Cα=Cβ-C4=C5 stretch coordinate, while that of MTCA was mostly along the Cα=Cβ and the C=O stretch motion. Comparison of the structural dynamics of M24PDA and MTCA with that of 3-methyl-3-pentene-2-one (3M3P2O) indicated that the structural dynamics of MTCA is similar to that of 3M3P2O but different than that of M24PDA in that the variation of the Raman intensity ratios for ν7/ν8, (ν7+ν8)/2ν8, (ν7+2ν8)/3ν8, (ν7+3ν8)/4ν8 of MTCA is similar to that of 3M3P2O but different from that of M24PDA. It is found that the substitution of methyl group in the α(')-position of α,β-enones by methoxyl group does not substantially affect the short-time structural dynamics, while the substitution of vinyl group in the β-position changes significantly the short-time structural dynamics and the subsequent decay processes. A detailed decay mechanism is proposed. Two sub-processes which consider the reconjugation and the subsequent charge-transfer reaction of O=C-Cα=Cβ chromophore were postulated to describe the variation of short-time structural dynamics with the different substitution.

The excited state structural dynamics of phenyl isothiocyanate (PITC) after excitation to the light absorbing S2(A'), S6(A'), and S7(A') excited states were studied by using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The UV absorption bands of PITC were assigned. The vibrational assignments were done on the basis of the Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 299.1, 282.4, 266.0, 252.7, 228.7, 217.8, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PITC. The results indicated that the structural dynamics in the S2(A'), S6(A'), and S7(A') excited states were very different. The conical intersection point CI(S2/S1) were predicted to play important role in the low-lying excited state decay dynamics. Two major decay channels were predicted for PITC upon excitation to the S2(A') state: the radiative S(2,min) → S0 transition and the nonradiative S2 → S1 internal conversion via CI(S2/S1). The differences in the decay dynamics between methyl isothiocyanate and PITC in the first light absorbing excited state were discussed. The role of the intersystem crossing point ISC(S1/T1) in the excited state decay dynamics of PITC is evaluated.

Density functional theory, UV absorption, and Raman spectroscopy are used to investigate the structure and properties of TDO in aqueous solution. The equilibrium structures, UV absorption spectra, interaction energies, and Raman spectroscopy data of TDO, AIMSA, and 12 TDO or AIMSA clusters are calculated. Raman spectroscopy experiments are carried out by 488 and 208 nm laser excitation. The Raman spectra of TDO in solid and aqueous phases have been compared, and the most possible structure for TDO in aqueous phase was deduced from analysis of the DFT calculations for the examined models, the experimental UV absorption spectrum, and Raman spectra of TDO. The interaction energy results show that TDO's solubility in water is originated from the TDO-water cyclic oligomer. The calculated UV absorption and Raman spectra of the I2·2H2O-cyc cluster model agree with the experimental results of TDO in aqueous solution very well.

An experimental study on the removal of Cu(II) from aqueous solutions by D151 resin was carried out in a batch system. The response surface methodology (RSM)-guided optimization indicated that the optimal adsorption conditions are: temperature of 35 °C, pH of 5.38, and initial Cu(II) concentration of 0.36 mg/mL, and the predicted adsorption capacity from the model reached 328.3 mg/g. At optimum adsorption conditions, the adsorption capacity of Cu(II) was 321.6 mg/g, which obtained from real experiments what were in close agreement with the predicted value. The adsorption isotherms data fitted the Langmuir model well, and the correlation coefficient has been evaluated. The calculation data of thermodynamic parameters (ΔG, ΔS, and ΔH) confirmed that the adsorption process was endothermic and spontaneous in nature. The desorption study revealed that Cu(II) can be effectively eluted by 1 mol/l HCl solution, and the recovery was 100%. Moreover, the characterization was undertaken by infrared (IR) spectroscopy.

The adsorption and desorption properties of D001 resin for Cd(II) has been investigated. Batch studies were carried out with various pH, contact time, temperature and initial concentrations, and then column studies were conducted. The results showed that the optimal adsorption condition was at pH value of 3.0 in HAc-NaAc medium. The resin exhibited a high Cd(II) uptake of 185.8 mg/g at 298 K. The apparent activation energy Ea is 5.05 kJ/mol and the sorption thermodynamic parameters are ΔH = 21.1 kJ/mol, ΔS = 0.122 kJ/(mol K) and ΔG298K = -15.3 kJ/mol, which indicated that the adsorption process was spontaneous and endothermic. Compared with the Freundlich isotherm, the sorption of Cd(II) obeys the Langmuir isotherm better. The Thomas model was delineated here to predict the breakthrough curves based on the experimental column study data. Furthermore, the resin could be regenerated through the desorption of the Cd(II) anions using 1 mol/L HCl solution and could be reused to adsorb again. The infrared spectroscopic technique was undertaken. Compared with other absorbents, D001 resin was relatively low cost and was effective in removing Cd(II) ions.

The reactions of iron and manganese monoxide molecules (FeO, and MnO) with monochloromethane in solid argon have been studied by matrix isolation infrared spectroscopy and quantum chemistry calculations. When annealing, the reactions of FeO and MnO with CH3Cl first form the OM-(η(Cl)-CH3Cl) (MMn, Fe) complexes, which can isomerize to CH3MOCl (MMn, Fe) upon 300<λ<580 nm irradiation. The products were characterized by isotopic IR studies with CD3Cl and (13)CH3Cl and density functional calculations. Based on theoretical calculations, the OFe-(η(Cl)-CH3Cl) and OMn-(η(Cl)-CH3Cl) complexes have (5)A' and (6)A' ground state with Cs symmetry, respectively. The accurate CCSD(T) single point calculations illustrate the CH3MOCl isomerism are 13.8 and 3.1 kcal/mol lower in energy than the OM-(η(Cl)-CH3Cl) (MMn, Fe) complexes., (Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.)

In this study, cross-linked chitosan microspheres (CCTS) was synthesized from chitosan and epichlorohydrin (ECH), then, 2-(chloromethyl) benzimidazole (CBM) was introduced to modify CCTS as the ligand. The resulting CBM-chitosan was characterized by EA, FTIR and TGA, and tested for metal adsorption. Results showed that CBM-chitosan has a relatively high selectivity toward Hg(2+). Equilibrium data were fitted well with Langmuir isotherms with the maximum adsorption capacity of 257.8 mg/g for Hg(2+). Both kinetics and thermodynamic parameters of the adsorption process were obtained. The data indicated that adsorption process was exothermic spontaneous reaction and kinetically proceeded according to Second-order kinetics model. CBM-chitosan can be eluted effectively using 1.0 mol/L HCl solution and it has a potential use for separation and preconcentration of Hg(2+) ions from contaminated natural waters., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The resonance Raman spectroscopic study of the excited state structural dynamics of 1,3-dimethyluracil (DMU), 5-bromo-1,3-dimethyluracil (5BrDMU), uracil, and thymine in water and acetonitrile were reported. Density functional theory calculations were carried out to help elucidate the ultraviolet electronic transitions associated with the A-, and B-band absorptions and the vibrational assignments of the resonance Raman spectra. The effect of the methylation at N1, N3 and C5 sites of pyrimidine ring on the structural dynamics of uracils in different solvents were explored on the basis of the resonance Raman intensity patterns. The relative resonance Raman intensities of DMU and 5BrDMU are computed at the B3LYP-TD level. Huge discrepancies between the experimental resonance Raman intensities and the B3LYP-TD predicted ones were observed. The underlying mechanism was briefly discussed. The decay channel through the S1((1)nπ*)/S2((1)ππ*) conical intersection and the S1((1)nπ*)/T1((3)ππ*) intersystem crossing were revealed by using the CASSCF(8,7)/6-31G(d) level of theory calculations.

The reactivity of nanoscale zerovalent iron (NZVI) on removing chlorophenols (2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol) was remarkably enhanced by using a hydrophobic support of organobentonite (CTMA-Bent), namely the bentonite modified with organic cetyltrimethylammonium (CTMA) cations. The complete dechlorination of chlorophenols and total conversion into phenol using this novel NZVI/CTMA-Bent combination was observed in batch experiments. The kinetic studies suggested that the reduction of chlorophenols by NZVI was accelerated due to the enhanced adsorption onto CTMA-Bent, which facilitated the mass transfer of chlorophenols from aqueous to iron surface. The enhanced reduction rate by NZVI/CTMA-Bent was positively related to the hydrophobicity of chlorophenols, and an increasing linear relationship was obtained between the relative enhancement on reaction rate constants (k2/k1) and logKow values of chlorophenols. XPS results suggested there were fewer precipitates of ferric (hydro)xides formed on the surface of NZVI/CTMA-Bent, which may also lead to the improved reactivity and repetitive usability of NZVI/CTMA-Bent on removing chlorophenols., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Resonance Raman (RR) spectra and quantum chemical calculations were used to investigate the photodissociation dynamics of propanil in the S2 state. The RR spectra indicate that the photorelaxation dynamics for the S0 → S2 excited state of propanil is predominantly along nine motions: C═O stretch, ν51 (1659 cm(-1)), ring C═C stretch, ν50 (1590 cm(-1)), NH wag/ring C═C stretch, ν49 (1534 cm(-1)), ring CCH in-plane bend/NH wag, ν42 (1383 cm(-1)), NH wag/-CH2- rock, ν41 (1353 cm(-1)), ring C═C stretch/NH wag/-CH2- rock in-plane, ν40 (1299 cm(-1)), Ph-NH stretch/ring CCH in-plane bend, ν37 (1236 cm(-1)), ring CCH in-plane bend, ν35 (1150 cm(-1)), -CH2CH3 twist, ν33 (1080 cm(-1)), ring trigonal bend, ν31 (1029 cm(-1)), ring CCH bend out-of-plane, ν27 (899 cm(-1)), whole skeleton deformation in-plane, ν20(688 cm(-1)). Strong electron coupling between S1 and S2 of propanil is found by quantum chemistry calculations and depolarization spectra. The excited-state dynamics of the S2 state is discussed, and the results are compared with the previously reported results for formanilide to examine the Cl substitution effect.

The optimized structural parameters, the absorption and the resonance Raman spectra have been investigated for the bis(2-thienyl)ketone in gas phase, in cyclohexane, methanol, and acetonitrile solvents by means of time dependent density functional theory calculations, the solvent electronic polarization effect on the solvation shift is examined and in well accordance with the calculation. The effect of increasing the polarity of the solvent is well represented by the polarizable continuum model, both for the absorption spectra and resonance Raman intensities. The Raman spectra of the C=O stretching mode, which is sensitive to the intermolecular interaction for bis(2-thienyl)ketone dissolved in solvents, were systematically studied. It was found that the hydrogen bond effect plays an important role in reducing the carbonyl stretching wavenumbers. The results of Raman shifts were interpreted through the dilution effect, solvation effects, and hydrogen bond-forming effects. Furthermore, the excitation profiles of several important Raman bands of bis(2-thienyl)ketone molecule in different solvents have been critically analyzed. The solvent effects on structural and symmetry properties of the molecule in S2 electronic state as well as the short-time photo relaxation dynamics have been discussed.

FT-Raman and/or FT-IR spectra of 3-amino-2-cyclohexen-1-one (ACyO) in solid state and/or in solvents of water and acetonitrile were obtained. Density functional theory calculations were done to help elucidate the vibrational band assignments. The A-band resonance Raman spectra of ACyO were acquired in water and acetonitrile solvents to examine the excited state structural dynamics and the state-mixing or curve-crossing tuned by solvents. A preliminary resonance Raman intensity analysis using the time-dependent wave-packet theory and simple model was done for ACyO in acetonitrile solvent. Resonance Raman spectroscopic probing of the excited state curve-crossing or state-mixing was proposed., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Carbon dioxide coordination and activation by niobium oxide molecules were studied by matrix isolation infrared spectroscopy. It was found that the niobium monoxide molecule reacted with carbon dioxide to form the niobium dioxide carbonyl complex NbO(2)(η(1)-CO) spontaneously on annealing in solid neon. The observation of the spontaneous reaction is consistent with theoretical predictions that this carbon dioxide activation process is both thermodynamically exothermic and kinetically facile. In contrast, four niobium dioxide-carbon dioxide complexes exhibiting three different coordination modes of CO(2) were formed from the reactions between niobium dioxide and carbon dioxide, which proceeded with the initial formation of the η(1)-O bound NbO(2)(η(1)-OCO) and NbO(2)(η(1)-OCO)(2) complexes on annealing. The NbO(2)(η(1)-OCO) complex rearranged to the η(2)-O,O bound NbO(2)(η(2)-O(2)C) isomer under visible light irradiation, while the NbO(2)(η(1)-OCO)(2) complex isomerized to the NbO(2)(η(1)-OCO)(η(2)-OC)O structure involving an η(2)-C,O ligand under IR excitation. In these niobium dioxide carbon dioxide complexes, the η(1)-O coordinated CO(2) ligand serves as an electron donor, whereas both the η(2)-C,O and η(2)-O,O coordinated CO(2) ligands act as electron acceptors.

Resonance Raman spectra (RRs) for 4,5-ethylenedithio-1,3-dithiole-2-thione (EDDT) were obtained with 397.9 and 416 nm excitation wavelengths, and density functional calculations were performed to elucidate the electronic transitions and the RRs of EDDT in chloroform solvent. The RRs indicate that the Franck-Condon region photodynamics have multidimensional character with nuclear motion predominantly along the C(4)═C(5) stretch and the C(4)═C(5) twist out-of-plane. Resonance Raman cross-sections of A-band absorption have been obtained for the vibrational modes of EDDT with its excitation frequencies spanning the 408 nm. Resonance Raman intensity analysis of the resulting RRs excitation profiles and absorption spectrum using a time-dependent wave packet formalism yields mode-specific nuclear displacement and vibrational reorganizational energies. The intensity analysis results for EDDT were compared to previously reported results for dimethyl 1,3-dithiole-2-thione-4,5-dicarboxylate (DDTD), which shows that the additional six-member heterocycle of EDDT strongly affects the reorganizational energy and energy participation. The authors briefly discuss the differences and similarities of the spectra in terms of molecular symmetry and electron density.

Nanoscale zero valent iron (NZVI) was immobilized on the organobentonite (CTMA-bent), so as to enhance the reactivity of NZVI and prevent its aggregation. This novel composite (NZVI/CTMA-Bent) was characterized by transmission electron microscope and X-ray diffraction. Good dispersion of NZVI particles on the bentonite was observed. Its performance on removing pentachlorophenol (PCP) was investigated by batch experiments. Results showed NZVI/CTMA-Bent could rapidly and completely dechlorinate PCP to phenol with an efficiency of 96.2%. It was higher than the sum (54.5%) of reduction by NZVI (31.5%) and adsorption by CTMA-Bent (23.0%) separately. The kinetic studies indicated the removal rate of PCP was positively related to the adsorption. We proposed that the adsorption of PCP by CTMA-Bent enhanced the mass transfer of PCP from aqueous to iron surface. Besides, NZVI/CTMA-Bent exhibited good stability and reusability, and CTMA-Bent could also reduce the amount of iron ions released into the solution., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The reactions of beryllium atoms with dioxygen were reinvestigated by matrix isolation infrared absorption spectroscopy. Besides the previously reported linear OBeO and cyclic Be(2)O(2) molecules, two interconvertible beryllium ozonide complexes were prepared and characterized. The BeOBe(η(2)-O(3)) complex was formed on annealing, which is characterized to be a side-on bonded ozonide complex with a planar C(2v) structure. The BeOBe(η(2)-O(3)) complex isomerized to the BeOBe(η(1)-O(3)) isomer under visible light excitation, which is an end-on bonded ozonide complex with planar C(s) symmetry. These two isomers are interconvertible; that is, visible light induces the conversion of the side-on bonded complex to the end-on bonded isomer, and vice versa on annealing. In addition, evidence is also presented for the linear BeOBeOBe cluster.

The resonance Raman spectra were obtained for both 2-thiopyridone (2TP) and its proton-transfer tautomer 2-mercaptopyridine (2MP) in water solution. Density functional theory (DFT) calculations were carried out to help elucidate their ultraviolet electronic transitions and vibrational assignments of the resonance Raman spectra associated with their B-band absorptions. The nanosecond time-resolved resonance Raman spectroscopic experiment was carried out to further confirm the assignment that the transient species was the ground state 2MP. The different short-time structural dynamics were examined for both 2TP and 2MP in terms of their resonance Raman intensity patterns. The transition barriers between 2TP and 2MP for S(0), T(1), and S(1) states are determined by using (U)B3LYP-TD and CASSCF level of theory computations, respectively. The excited state proton transfer (ESPT) reaction mechanism is proposed and briefly discussed.

The reactions of titanium oxide molecules with dinitrogen have been studied by matrix isolation infrared spectroscopy. The titanium monoxide molecule reacts with dinitrogen to form the TiO(N(2))(x) (x = 1-4) complexes spontaneously on annealing in solid neon. The TiO(η(1)-NN) complex is end-on bonded and was predicted to have a (3)A'' ground state arising from the (3)Δ ground state of TiO. Argon doping experiments indicate that TiO(η(1)-NN) is able to form complexes with one or more argon atoms. Argon atom coordination induces a large red-shift of the N-N stretching frequency. The TiO(η(2)-N(2))(2) complex was characterized to have C(2v) symmetry, in which both the N(2) ligands are side-on bonded to the titanium metal center. The tridinitrogen complex TiO(η(1)-NN)(3) most likely has C(3v) symmetry with three end-on bonded N(2) ligands. The TiO(η(1)-NN)(4) complex was determined to have a C(4v) structure with four equivalent end-on bonded N(2) ligands. In addition, evidence is also presented for the formation of the TiO(2)(η(1)-NN)(x) (x = 1-4) complexes, which were predicted to be end-on bonded.

The 397.9 nm, 416.0 nm and 435.7 nm resonance Raman spectra were acquired for meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in tetrahydrofuran solution, and the Raman effect of relaxation dynamics was analyzed according to Herzberg-Teller (vibronic coupling) contributions. Density functional calculations were done to help the elucidation of the Soret (B(x) and B(y)-band) electronic transitions and the corresponding photo relaxation dynamics of TCPP. The spectra indicate that the Franck-Condon region photo relaxation dynamics upon S(0) → S(4) electronic transition are predominantly along the totally symmetric C(m)-ph stretch and Porphin ring breath stretch, and simultaneously along the asymmetric ν(C(m)-Phenyl) + δ(N-H) and ν(C(α)-C(m)-C(α))(as) + def (pyr) vibrational relaxation processes. The excited state structural dynamics of TCPP determined from the resonance Raman spectra show that the internal conversion between the B(y) and B(x) electronic states occurs in tens of femtoseconds, and the electronic relaxation dynamics were firstly interpreted taking into account the time-dependent wave packet theory and Herzberg-Teller (vibronic coupling) contributions.

Resonance Raman spectra of free-base octaethylporphine (OEP) were obtained with 368.9 nm, 397.9 nm and 416.0 nm excitation wavelengths, and density functional calculations were done to help the elucidation of Soret (B(x) and B(y)-band) electronic transitions and the corresponding photo relaxation dynamics of OEP. The RRs indicate that the Franck-Condon region photo relaxation dynamics upon S(0)→S(8) electronic transition is predominantly along the totally symmetric C(m)C(α) stretch, the C(β)C(β) stretch, and simultaneously along the asymmetric δ(pyr deformation),γ(CH(2)) vibrational relaxation processes. The excited state structural dynamics of OEP determined from resonance Raman spectra show that the internal conversion between B(y) and B(x) electronic states occurs in tens of femtoseconds and the electronic relaxation dynamics were firstly interpreted with account of the time-dependent wave packet theory and Herzberg-Teller (vibronic coupling) contributions., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The reactions of group V metal dioxide molecules with dihydrogen have been studied by matrix isolation infrared spectroscopy. The ground state VO(2) molecule is able to cleave dihydrogen heterolytically and spontaneously in forming the HVO(OH) molecule in solid argon. In contrast, the reaction of VO(2) with dideuterium to form DVO(OD) proceeds only under UV-visible excitation via a weakly bound VO(2)(η(2)-D(2)) complex. Theoretical calculations predict that the dihydrogen cleavage process is thermodynamically exothermic with a small barrier. The niobium and tantalum dioxide molecules react with dihydrogen to give primarily the side-on bonded metal dioxide bis-dihydrogen complexes, NbO(2)(η(2)-H(2))(2) and TaO(2)(η(2)-H(2))(2), which are further transferred to the HNbO(OH) and HTaO(OH) molecules via photoisomerization in combination with H(2) elimination under UV-visible light excitation.