Direct observation of the 4-methoxyphenylnitrene intersystem crossing from S1 to T1 using picosecond Kerr-gated time-resolved resonance Raman spectroscopy

A picosecond Kerr-gated time-resolved resonance Raman (ps-KTR(3)) study of the singlet 4-methoxyphenylnitrene intersystem crossing to produce the triplet 4-methoxyphenylnitrene species is reported. The experimental resonance Raman vibrational band frequencies observed for the singlet and triplet 4-methoxylphenylnitrene species in the time-resolved Raman experiments are compared to each other and to predictions from previously published density functional theory calculations. The structure, properties, and chemical reactivity of the singlet and triplet states of the 4-methoxyphenylnitrenes are briefly discussed.     

Reaction of the 4-biphenylnitrenium ion with 4-biphenyl azide to produce a 4,4'-azobisbiphenyl stable product: a time-resolved resonance Raman and density functional theory study

A time-resolved resonance Raman (TR(3)) and density functional theory (DFT) study of the reaction of the 4-biphenylnitrenium ion with 4-biphenyl azide in a mixed aqueous solution is reported. The reaction of the 4-biphenylnitrenium ion with its unphotolyzed precursor 4-biphenyl azide in a mixed aqueous solution generates a 4,4'-azobisbiphenyl stable product via an intermediate species. With the aid of DFT calculations for likely transient species, this intermediate was tentatively assigned to a 4,4'-azobisbiphenyl cation. The DFT calculations predict this reaction can take place via two pathways that compete with one another to produce the trans and cis 4,4'-azobisbiphenyl product. The observation of the 4,4'-azobisbiphenyl cation intermediate demonstrates that the reaction of the arylnitrenium ion with its aryl azide to produce a stable azo product occurs via a stepwise mechanism.     

Simultaneous detection of two triplets: a time-resolved resonance Raman study

Solvents are known to affect the triplet state structure and reactivity. In this paper, we have employed time-resolved resonance Raman (TR3) spectroscopy to understand solvent-induced subtle structural changes in the lowest excited triplet state of thioxanthone. Density functional theory (DFT) combined with the self-consistent reaction field (SCRF) implicit solvation model has been used to calculate the vibrational frequencies in the solvents. Here, we report a unique observation of the coexistence of two triplets, which has been substantiated by the probe wavelength-dependent Raman experiments. The coexistence of two triplets has been further supported by photoreduction experiments carried out at various temperatures.     

Direct dynamics study on hydrogen abstraction reaction of CF3CF2CH2OH with OH radical

The dual-level direct dynamics method has been employed to investigate the H-abstraction reaction of CF(3)CF(2)CH(2)OH with OH radical, which is predicted to have two classes of possible reaction channels caused by different positions of hydrogen atom attack. The minimum-energy path is calculated at the B3LYP/6-311G(d,p) level, and the energetic information is further refined by the MC-QCISD method. To compare the structures, the other method MPW1K/6-311G(d,p) is also applied to this system. Hydrogen-bonded complexes are presented in the reactant and product sides of the three channels, indicating that each reaction may proceed via an indirect mechanism. The rate constants for each reaction channel are evaluated by canonical variational transition-state theory (CVT) with the small-curvature tunneling correction (SCT) over a wide range of temperatures from 200 to 2000 K. The calculated CVT/SCT rate constants are found to be in good agreement with the available experimental values. The result shows that the variational effect is small, and in the lower-temperature range, the SCT effect is important for each reaction. It is shown that hydrogen abstracted from the -CH(2)- position is the major channel, while H-abstraction from the -OH position may be neglected with the temperature increasing.     

Time-resolved resonance Raman and density functional study of an azirine intermediate in the 2-fluorenylnitrene ring-expansion reaction to form a dehydroazepine product

We report time-resolved resonance Raman spectra for the azirine intermediate produced in the 2-fluorenylnitrene ring-expansion reaction to form a dehydroazepine product. The Raman bands obtained with a 252.7 nm probe wavelength and 500 ns delay time exhibit reasonable agreement with predicted vibrational frequencies from density functional calculations for two isomers of azirine intermediates that may be formed from a 2-fluorenylnitrene precursor. The Raman bands observed for delay times of 15 ns and 10 micros were consistent with predicted vibrational frequencies from density functional calculations for the 2-fluorenylnitrene and dehydroazepine product species as well as previously reported 416 nm time-resolved Raman spectra obtained on the ns and micros time scales. Our results demonstrate that the 2-fluorenylnitrene ring-expansion reaction to produce dehydroazepine products proceeds via relatively long-lived 2-fluorenylnitrene and azirine intermediates. Substitution of a phenyl ring para to the nitrene group of phenylnitrene appears to lead to significant changes in the ring-expansion reaction so that longer lived arylnitrene and azirine intermediates can be observed. This should enable the chemical reactivity of azirine intermediates formed from arylnitrenes to be examined more readily.     

Theoretical study and rate constant calculation for reaction of CF(3)CH(2)OH with OH

The reaction mechanism of CF(3)CH(2)OH with OH is investigated theoretically and the rate constants are calculated by direct dynamics method. The potential energy surface (PES) information, which is necessary for dynamics calculation, is obtained at the B3LYP/6-311G (d, p) level. The single-point energy calculations are performed at the MC-QCISD level using the B3LYP geometries. Complexes, with the energies being less than corresponding reactants and products, are found at the entrance and exit channels for methylene-H-abstraction channel, while for the hydroxyl-H-abstraction channel only entrance complex is located. By means of isodesmic reactions, the enthalpies of the formation for the species CF(3)CH(2)OH, CF(3)CHOH, and CF(3)CH(2)O are estimated at the MC-QCISD//B3LYP/6-311G (d, p) level of theory. The rate constants for two kinds of H-abstraction channels are evaluated by canonical variational transition state theory with the small-curvature tunneling correction (CVT/SCT) over a wide range of temperature 200-2000 K. The calculated results are in good agreement with the experimental values in the temperature region 250-430 K. The present results indicate that the two channels are competitive. Below 289 K, hydroxyl-H-abstraction channel has more contribution to the total rate constants than methylene-H-abstraction channel, while above 289 K, methylene-H-abstraction channel becomes more important and then becomes the major reaction channel.     

Direct measurement of S-branch N(2)-H(2) Raman linewidths using time-resolved pure rotational coherent anti-Stokes Raman spectroscopy

S-branch N(2)-H(2) Raman linewidths have been measured in the temperature region 294-1466 K using time-resolved dual-broadband picosecond pure rotational coherent anti-Stokes Raman spectroscopy (RCARS). Data are extracted by mapping the dephasing rates of the CARS signal temporal decay. The J-dependent coherence decays are detected in the time domain by following the individual spectral lines as a function of probe delay. The linewidth data set was employed in spectral fits of N(2) RCARS spectra recorded in binary mixtures of N(2) and H(2) at calibrated temperature conditions up to 661 K using a standard nanosecond RCARS setup. In this region, the set shows a deviation of less than 2% in comparison with thermocouples. The results provide useful knowledge for the applicability of N(2) CARS thermometry on the fuel-side of H(2) diffusion flames.     

.OH radical reaction with CH2Cl2: Direct spectrophotometric observation of.CHCl2 radical formation

Hydrogen abstraction from methylene chloride by the^.OH radical in aqueous solution is monitored by direct observation of the^.CHCl₂ radical absorption build-up at 220 nm, yielding a bimolecular rate constant of /5.8±0.2/xlo⁷ M^–1s^–1 at room temperature. A spectral band extending from 220 nm to 330 nm is assigned to the dichloromethyl radical.     

Kinetics and mechanism of (CF3)2CHOCH3 reaction with OH radicals in an environmental reaction chamber

The atmospheric chemistry of (CF3)2CHOCH3, a possible HCFC/HFC alternative, was studied using a smog chamber/FT-IR technique. OH radicals were prepared by the photolysis of ozone in a 200-Torr H2O/O3/O2 gas mixture held in an 11.5-dm3 temperature-controlled chamber. The rate constant, k1, for the reaction of (CF3)2CHOCH3 with OH radicals was determined to be (1.40 +/- 0.28) x 10(-12) exp[(-550 +/- 60)/T] cm3 molecule(-1) s(-1) by means of a relative rate method at 253-328 K. The value of k1 at 298 K was (2.25 +/- 0.04) x 10(-13) cm3 molecule(-1) s(-1). The random errors are reported with +/-2 standard deviations, and potential systematic errors of 15% could increase k(1). In considering OH-radical reactions, we estimated the tropospheric lifetime of (CF3)2CHOCH3 to be 2.0 months using the rate constant at 288 K. The degradation mechanism of (CF3)2CHOCH3 initiated by OH radicals was also investigated using FT-IR spectroscopy at 298 K. Products (CF3)2CHOC(O)H, CF3C(OH)2CF3, CF3C(O)OCH3, and COF(2) were identified and quantified. The branching ratio, k1a/k1b, was estimated to be 2.1:1 for reactions (CF3)2CHOCH3 + OH --> (CF3)2CHOCH2*+ H2O (k1a) and (CF3)2CHOCH3 + OH --> (CF3)2C*OCH3 + H2O (k1b).     

Ultraviolet photolysis of CH2I2 in methanol: O-H insertion and HI elimination reactions to form a dimethoxymethane product

Ultraviolet photolysis of low concentrations of CH2I2 in methanol solution found that CH2I2 is converted into dimethoxymethane and some H+ and I- products. Picosecond time-resolved resonance Raman (ps-TR3) experiments observed that the isodiiodomethane (CH2I-I) photoproduct decayed faster as the concentration of methanol increases, suggesting that isodiiodomethane is reacting with methanol. Ab initio calculations indicate isodiiodomethane is able to react with methanol via an O-H insertion/HI elimination to form an iodoether (ICH2-O-CH3) and HI products. The iodoether can then further react via another O-H insertion/HI elimination reaction to form the dimethoxymethane (CH3-O-CH2-O-CH3) observed in the photochemistry experiments. A reaction mechanism consistent with these experimental and theoretical observations is proposed.     

Revealing the photophysics of fac-[(dppz-12-NO2)Re(CO)3(4-Me2Npy)]+: a picosecond time-resolved IR study

The photophysics of fac-[(dppz-12-NO2)Re(CO)3(4-Me2Npy)]+ in CH3CN have been investigated using picosecond time-resolved IR (ps-TRIR) spectroscopy, to reveal the first example of a Re(I)-dppz complex with a charge separated lowest-lying excited state.     

Computational study of the reaction of CH2(X3B1) with CH3OH

The reaction of triplet methylene with methanol is a key process in alcohol combustion but surprisingly this reaction has never been studied. The reaction mechanism is investigated by using various high-level ab initio methods, including the complete basis set extrapolation (CBS-QB3 and CBS-APNO), the latest Gaussian-n composite method (G4), and the Weizmann-1 method (W1U). A total of five product channels and six transition states are found. The dominant mechanism is direct hydrogen abstraction, and the major product channel is CH(3) + CH(3)O, involving a weak prereactive complex and a 7.4 kcal/mol barrier. The other hydrogen abstraction channel, CH(3) + CH(2)OH, is less important even though it is more exothermic and involves a similar barrier height. The rate coefficients are predicted in the temperature range 200-3000 K. The tunneling effect and the hindered internal rotational freedoms play a key role in the reaction. Moreover, the reaction shows significant kinetic isotope effect.     

Competitive O-H and C-H oxidative addition of CH3OH to rhodium(II) porphyrins

Rhodium(II) porphyrins react with CH(3)OH in benzene by alternate mechanisms that give H-CH(2)OH and H-OCH(3) bond activation in different methanol concentration regimes which is a rare example of transition metal reactivity with methanol.     

First direct observation of a CO-bridged primary photoproduct of [Ru3(CO)12] by picosecond time-resolved IR spectroscopy

For the first time, a CO-bridged primary photoproduct was observed for [Ru3(CO)12] by using picosecond time-resolved IR spectroscopy (ps-TRIR).     

Raman spectroscopic study of the uranyl minerals vanmeersscheite U(OH)4[(UO2)3(PO4)2(OH)2].4H2O and arsenouranylite Ca(UO2)[(UO2)3(AsO4)2(OH)2].(OH)2.6H2O

Raman and infrared spectra of secondary uranyl phosphate vanmeersscheite and Raman spectrum of secondary uranyl arsenate arsenuranylite were recorded and interpreted, and the spectra related to the structure of the minerals. Observed bands were attributed to the stretching and bending vibrations of uranyl, phosphate and/or arsenate units and OH (H(2)O and OH(-)) units. Phosphuranylite sheet topology is characteristic for both minerals. U-O bond lengths in uranyl were calculated from the spectra and compared with those inferred for vanmeersscheite from the X-ray single crystal structure analysis. O-H...O hydrogen bonds in both minerals were also inferred using the Libowitzky empirical relation.     

Time-resolved resonance Raman observation of the 2-fluorenylnitrenium ion reaction with guanosine to form a C8 intermediate

Time-resolved resonance Raman spectroscopy was used to directly observe the reaction of the 2-fluorenylnitrenium ion with guanosine to produce a C8 intermediate species. Comparison of the Raman spectra with results of density functional theory calculations indicates the C8 intermediate forms two C=N conjugated bonds in ring 1 of the guanosine moiety.     

Mechanisms for the deamination reaction of cytosine with H2O/OH(-) and 2H2O/OH(-): a computational study

Mechanisms for the deamination reaction of cytosine with H 2O/OH (-) and 2H 2O/OH (-) to produce uracil were investigated using ab initio calculations. Optimized geometries of reactants, transition states, intermediates, and products were determined at MP2 and B3LYP using the 6-31G(d) basis set and at B3LYP/6-31+G(d) levels of theory. Single point energies were also determined at MP2/G3MP2Large and G3MP2 levels of theory. Thermodynamic properties (Delta E, Delta H, and Delta G), activation energies, enthalpies, and free energies of activation were calculated for each reaction pathway investigated. Intrinsic reaction coordinate (IRC) analysis was performed to characterize the transition states on the potential energy surface. Seven pathways for the deamination reaction were found. All pathways produce an initial tetrahedral intermediate followed by several conformational changes. The final intermediate for all pathways dissociates to product via a 1-3 proton shift. The activation energy for the rate-determining step, the formation of the tetrahedral intermediate for pathway D, the only pathway that can lead to uracil, is 115.3 kJ mol (-1) at the G3MP2 level of theory, in excellent agreement with the experimental value (117 +/- 4 kJ mol (-1)).     

Direct observation of competitive ultrafast CO dissociation and relaxation of an MLCT excited state: picosecond time-resolved infrared spectroscopic study of [Cr(CO)(4)(2,2'-bipyridine)

Early excited-state dynamics of [Cr(CO)(4)(bpy)] were studied in a CH(2)Cl(2) solution by picosecond time-resolved IR spectroscopy, which made it possible to characterize structurally the individual species involved and to follow separately the temporal evolution of the IR bands due to the bleached ground-state absorption, the fac-[Cr(CO)(3)(Sol)(bpy)] photoproduct, and two (3)MLCT states. It was found that the fac-[Cr(CO)(3)(Sol)(bpy)] photoproduct is formed alongside population of two (3)MLCT states during the first picosecond after excitation at 400 or 500 nm by a branched evolution of the optically populated excited state. Vibrationally relaxed (3)MLCT excited states are unreactive, decaying directly to the ground state on a picosecond time scale. The photoproduct is long-lived, persistent into the nanosecond time domain. Changing the excitation wavelength from 400 to 500 nm strongly increases the extent of the bleach recovery and decreases the yield of the photoproduct formation relative to the initial yield of the population of the unreactive (3)MLCT states. The photochemical quantum yield of CO dissociation also decreases with increasing excitation wavelength (Víchová, J.; Hartl, F.; Vlcek, A., Jr. J. Am. Chem. Soc. 1992, 114, 10903). These observations demonstrate the relationship between the early dynamics of optically populated excited states and the overall outcome of a photochemical reaction and identify the limiting role of the branching of the initial excited-state evolution between reactive and relaxation pathways as a more general principle of organometallic photochemistry.     

Time-resolved resonance Raman study of the reaction of the 2-fluorenylnitrenium ion with 2-fluorenylazide

A time-resolved resonance Raman investigation of the reaction of the 2-fluorenylnitrenium ion with 2-fluorenylazide in a mixed aqueous solvent is presented. The reaction of the 2-fluorenylnitrenium ion with 2-fluorenylazide in the mixed aqueous solution generates two new species on the microsecond time scale. One of these species is identified as 2,2'-azobisfluorene, and the other species is tentatively assigned to a 1,4-bis-(2,2'-fluorenyl)-tetrazadiene cation intermediate. The structure and properties of these two species are briefly discussed. The reaction of the 2-fluorenylnitrenium ion with 2-fluorenylazide is also briefly compared to that of the 2-fluorenylnitrenium ion reactions with guanosine and water.