Chloroacetone photodissociation at 193 nm and the subsequent dynamics of the CH3C(O)CH2 radical--an intermediate formed in the OH + allene reaction en route to CH3 + ketene

We use a combination of crossed laser-molecular beam experiments and velocity map imaging experiments to investigate the primary photofission channels of chloroacetone at 193 nm; we also probe the dissociation dynamics of the nascent CH(3)C(O)CH(2) radicals formed from C-Cl bond fission. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence another photodissociation channel of the precursor, C-C bond fission to produce CH(3)CO and CH(2)Cl. The CH(3)C(O)CH(2) radical formed from C-Cl bond fission is one of the intermediates in the OH + allene reaction en route to CH(3) + ketene. The 193 nm photodissociation laser allows us to produce these CH(3)C(O)CH(2) radicals with enough internal energy to span the dissociation barrier leading to the CH(3) + ketene asymptote. Therefore, some of the vibrationally excited CH(3)C(O)CH(2) radicals undergo subsequent dissociation to CH(3) + ketene products; we are able to measure the velocities of these products using both the imaging and scattering apparatuses. The results rule out the presence of a significant contribution from a C-C bond photofission channel that produces CH(3) and COCH(2)Cl fragments. The CH(3)C(O)CH(2) radicals are formed with a considerable amount of energy partitioned into rotation; we use an impulsive model to explicitly characterize the internal energy distribution. The data are better fit by using the C-Cl bond fission transition state on the S(1) surface of chloroacetone as the geometry at which the impulsive force acts, not the Franck-Condon geometry. Our data suggest that, even under atmospheric conditions, the reaction of OH with allene could produce a small branching to CH(3) + ketene products, rather than solely producing inelastically stabilized adducts. This additional channel offers a different pathway for the OH-initiated oxidation of such unsaturated volatile organic compounds, those containing a C=C=C moiety, than is currently included in atmospheric models.     

Ab initio studies for the photodissociation mechanism of hydroxyacetone

The reaction pathways for CH(3)COCH(2)OH (hydroxyacetone) photodissociation on the low-lying electronic states have been studied with use of the CASSCF energy gradient techniques. The S(0)/S(1) and S(1)/T(1) intersection points were determined by the state-average CASSCF method. Two main reaction pathways, which are possible to the photodissociation, have been studied. It has been found that the mechanism is stepwise, and belongs to Norrish type-I reaction. The n --> pi* excitation leads to the first excited singlet state, followed by the intersystem crossing from S(1) to T(1). On the T(1) potential energy surface, the system can dissociate adiabatically to CH(3)(x) +COCH(2)OH( x) and CH(3)CO(x)+CH(2)OH(x). The COCH(2)OH(x) and CH(3)CO(x) radicals can further dissociate into CO, OH, and other fragments. Our calculated results are in good agreement with recent experimental results.     

Photolysis of 4-oxo-2-pentenal in the 190-460 nm region

We have studied the gas-phase photolysis of 4-oxo-2-pentenal by laser photolysis combined with cavity ring-down spectroscopy. Absorption cross sections of cis- and trans-4-oxo-2-pentenal have been measured in the 190-460 nm region. The product channel following 193, 248, 308, and 351 nm photolysis of 4-oxo-2-pentenal was investigated. The HCO radical is a photodissociation product of 4-oxo-2-pentenal only at 193 and 248 nm. The HCO quantum yields from the photolysis of a mainly trans-4-oxo-2-pentenal sample are 0.13 +/- 0.02 and 0.014 +/- 0.003 at 193 and 248 nm, where errors quoted (1sigma) represent experimental scatter. The HCO quantum yields from the photolysis of a mainly cis-4-oxo-2-pentenal sample are 0.078 +/- 0.012 and 0.018 +/- 0.007 at 193 and 248 nm, where errors quoted (1sigma) represent experimental scatter. The end-products from 193, 248, 308, and 351 nm photolysis of 4-oxo-2-pentenal (the 4-oxo-2-pentenal sample had a tran/cis ratio of 1.062:1) have been determined by FTIR. Ethane, methyl vinyl ketone, and 5-methyl-3H-furan-2-one have been observed, suggesting the occurrence of 4-oxo-2-pentenal photolysis pathways such as CH(3)COCH=CHCHO + hnu --> CH(3) + COCH=CHCHO, CH(3)COCH=CHCHO + hnu --> CH(3)COCH=CH(2) + CO, and CH(3)COCH=CHCHO + hnu --> 5-methyl-3H-furan-2-one. The estimated yields for the CH(3) + COCH=CHCHO channel are about 25%, 33%, 31%, and 23% at 193, 248, 308, and 351 nm, respectively. The absolute uncertainties in the determination of CH(3) + COCH=CHCHO yields are within 55% at 193 nm, and 65% at 248, 308, and 351 nm. The estimated yields for the CH(3)COCH=CH(2) + CO channel are about 25%, 23%, 40%, and 33% at 193, 248, 308, and 351 nm, respectively. The absolute uncertainties in the determination of CH(3)COCH=CH(2) yields are within 80% at 193 and 248 nm and 65% at 308 and 351 nm. The estimated yields for the 5-methyl-3H-furan-2-one channel are about 1.2%, 2.1%, 5.3%, and 5.5% at 193, 248, 308, and 351 nm, respectively. The absolute uncertainties in the determination of 5-methyl-3H-furan-2-one yields are about 23%, 86%, 40%, and 46% at 193, 248, 308, and 351 nm. Results from our investigation indicate that photolysis is a dominant removal pathway for 4-oxo-2-pentenal degradation in the atmosphere.     

A 193 nm laser photofragmentation time-of-flight mass spectrometric study of chloroiodomethane

The photodissociation dynamics of chloroiodomethane (CH2ICl) at 193 nm has been investigated by employing the photofragment time-of-flight (TOF) mass spectrometric method. Using tunable vacuum ultraviolet undulator synchrotron radiation for photoionization sampling of nascent photofragments, we have identified four primary dissociation product channels: CH2Cl + I(2P(1/2))/I(2P(3/2)), CH2I + Cl(2P(1/2))/Cl(2P(3/2)), CHI + HCl, and CH2 + ICl. The state-selective detection of I(2P(3/2)) and I(2P(1/2)) has allowed the estimation of the branching ratio for I(2P(1/2)):I(2P(3/2)) to be 0.73:0.27. Theoretical calculations based on the time-dependent density-functional theory have been also made to investigate excited electronic potential-energy surfaces, plausible intermediates, and transition structures involved in these photodissociation reactions. The translation energy distributions derived from the TOF measurements suggest that at least two dissociation mechanisms are operative for these photodissociation processes. One involves the direct dissociation from the 2 1A' state initially formed by 193 nm excitation, leading to significant kinetic-energy releases. For the I-atom and Cl-atom elimination channels, the fragment kinetic-energy releases observed via this direct dissociation mechanism are consistent with those predicted by the impulsive dissociation models. Other mechanisms are likely predissociative or statistical in nature from the lower 1 1A' and 1 1A' states and/or the ground X 1A' state populated by internal conversion from the 2 1A' state. On the basis of the maximum kinetic-energy release for the formation of CH2Cl + I(2P(1/2)), we have obtained a value of 53+/-2 kcal/mol for the 0 K bond dissociation energy of I-CH2Cl. The intermediates and transition structures for the CHI + HCl and CH2 + ICl product channels have been also investigated by ab initio quantum calculations at the MP2(full)/6-311G(d) and B3LYP(full)/6-11G(d) levels of theory. The maximum kinetic-energy releases observed for the CHI + HCl and CH2 + ICl channels are consistent with the interpretation that the formation of CHI and CH2 in their ground triplet states is not favored.     

Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing the photodissociation and depopulating the excited S(2) or S(3) state molecules to the lowest T(1) state with a rate of ～2.5 ps after a delayed onset of ～3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T(1) excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T(1) excited state. The measured ultrafast formation of T(1) excited state supports the existence of the surface intersections of S(2)/S(1), S(2)/T(2), and S(1)/T(1)/T(2), and the large T(1) quantum yield of ～0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.     

叠氮化氰的光解离机理

采用多参考态方法,在MRCI+Q//CAS(10,9)/6-311+G(2df)水平上对叠氮化氰(N3CN)的光解离机理进行理论研究.优化得到基态(S0)和低激发态(S1、S2、T1)势能面上的极小点、过渡态、内转换交叉点(IC-S1/S0)和隙间窜跃交叉点(ISC-S1/T1)的结构和能量,构建反应势能面.在MRCI+Q//CAS(10,9)水平上计算N3CN的垂直激发能,并和实验值进行对比.结果表明,在S0、S1、S2和T1态势能面上,N—N键断裂生成N2+NCN是主要解离途径,而C—N键断裂通道是次要通道.实验观测到220 nm处的吸收峰对应分子由S0态到S1态的激发,对应主要光解离产物为NCN[a1△g];而在275 nm处的吸收峰则对应分子被激发到T1态,然后直接生成基态产物NCN[X3Σg-].我们的理论结果与实验测量符合得很好.     

Photodissociation pathways of 1,1-dichloroacetone

We present a comprehensive investigation of the dissociation dynamics following photoexcitation of 1,1-dichloroacetone (CH(3)COCHCl(2)) at 193 nm. Two major dissociation channels are observed: cleavage of a C-Cl bond to form CH(3)C(O)CHCl + Cl and elimination of HCl. The branching between these reaction channels is roughly 9:1. The recoil kinetic energy distributions for both C-Cl fission and HCl elimination are bimodal. The former suggests that some of the radicals are formed in an excited electronic state. A portion of the CH(3)C(O)CHCl photoproducts undergo secondary dissociation to give CH(3) + C(O)CHCl. Photoelimination of Cl(2) is not a significant product channel. A primary C-C bond fission channel to give CH(3)CO + CHCl(2) may be present, but this signal may also be due to a secondary dissociation. Data from photofragment translational spectroscopy with electron impact and photoionization detection, velocity map ion imaging, and UV-visible absorption spectroscopy are presented, along with G3//B3LYP calculations of the bond dissociation energetics.     

丙烯酰氯分子的气相光解动力学

利用时间分辨傅立叶变换红外(TR-FTIR)发射光谱研究了气相中CH2=CHCOCl分子的光解动力学.观测到振动激发的光解碎片分子CO(ν≤5),HCl(ν≤6),C2H2和相应的两个光解离通道:C-Cl键断裂和HCl消除通道.通过分析转动分辨的红外发射光谱得到CO和HCl的初始振转能量态分布,由此提出CH2=CHCOCl的气相光解机理并阐明了内转换等非绝热过程在影响反应途径中的关键作用.     

Analyzing velocity map images to distinguish the primary methyl photofragments from those produced upon C-Cl bond photofission in chloroacetone at 193 nm

We use a combination of crossed laser-molecular beam scattering experiments and velocity map imaging experiments to investigate the three primary photodissociation channels of chloroacetone at 193 nm: C-Cl bond photofission yielding CH(3)C(O)CH(2) radicals, C-C bond photofission yielding CH(3)CO and CH(2)Cl products, and C-CH(3) bond photofission resulting in CH(3) and C(O)CH(2)Cl products. Improved analysis of data previously reported by our group quantitatively identifies the contribution of this latter photodissociation channel. We introduce a forward convolution procedure to identify the portion of the signal, derived from the methyl image, which results from a two-step process in which C-Cl bond photofission is followed by the dissociation of the vibrationally excited CH(3)C(O)CH(2) radicals to CH(3) + COCH(2). Subtracting this from the total methyl signal identifies the methyl photofragments that result from the CH(3) + C(O)CH(2)Cl photofission channel. We find that about 89% of the chloroacetone molecules undergo C-Cl bond photofission to yield CH(3)C(O)CH(2) and Cl products; approximately 8% result in C-C bond photofission to yield CH(3)CO and CH(2)Cl products, and the remaining 2.6% undergo C-CH(3) bond photofission to yield CH(3) and C(O)CH(2)Cl products.     

Combined vacuum ultraviolet laser and synchrotron pulsed field ionization study of CH2BrCl

The pulsed field ionization-photoelectron (PFI-PE) spectrum of bromochloromethane (CH2BrCl) in the region of 85,320-88,200 cm-1 has been measured using vacuum ultraviolet laser. The vibrational structure resolved in the PFI-PE spectrum was assigned based on ab initio quantum chemical calculations and Franck-Condon factor predictions. At energies 0-1400 cm-1 above the adiabatic ionization energy (IE) of CH2BrCl, the Br-C-Cl bending vibration progression (nu1+=0-8) of CH2BrCl+ is well resolved and constitutes the major structure in the PFI-PE spectrum, whereas the spectrum at energies 1400-2600 cm-1 above the IE(CH2BrCl) is found to exhibit complex vibrational features, suggesting perturbation by the low lying excited CH2BrCl+(A 2A") state. The assignment of the PFI-PE vibrational bands gives the IE(CH2BrCl)=85,612.4+/-2.0 cm-1 (10.6146+/-0.0003 eV) and the bending frequencies nu1+(a1')=209.7+/-2.0 cm-1 for CH2BrCl+(X2A'). We have also examined the dissociative photoionization process, CH2BrCl+hnu-->CH2Cl++Br+e-, in the energy range of 11.36-11.57 eV using the synchrotron based PFI-PE-photoion coincidence method, yielding the 0 K threshold or appearance energy AE(CH2Cl+)=11.509+/-0.002 eV. Combining the 0 K AE(CH2Cl+) and IE(CH2BrCl) values obtained in this study, together with the known IE(CH2Cl), we have determined the 0 K bond dissociation energies (D0) for CH2Cl+-Br (0.894+/-0.002 eV) and CH2Cl-Br (2.76+/-0.01 eV). We have also performed CCSD(T, full)/complete basis set (CBS) calculations with high-level corrections for the predictions of the IE(CH2BrCl), AE(CH2Cl+), IE(CH2Cl), D0(CH2Cl+-Br), and D0(CH2Cl-Br). The comparison between the theoretical predictions and experimental determinations indicates that the CCSD(T, full)/CBS calculations with high-level corrections are highly reliable with estimated error limits of <17 meV.     

Photodissociation of propargyl chloride at 193 nm

The photodissociation of propargyl chloride (C3H3Cl) has been studied at 193 nm. Ion imaging experiments with state-selective detection of the Cl atoms and single-photon ionization of the C3H3 radicals were performed, along with measurements of the Cl + C3H3 and HCl + C3H2 recoil kinetic energy distributions, using a scattering apparatus with electron bombardment ionization detection to resolve the competing Cl and HCl elimination channels. The experiments allow the determination of the Cl (2P3/2) and Cl (2P1/2) (hereafter Cl) branching fractions associated with the C-Cl bond fission, which are determined to be 0.5 +/- 0.1 for both channels. Although prior translational spectroscopy studies by others had concluded that the low velocity signal at the Cl+ mass was due to daughter fragments of the HCl elimination products, the present work shows that Cl atoms are produced with a bimodal recoil kinetic energy distribution. The major C-Cl bond fission channel, with a narrow recoil kinetic energy distribution peaking near 40 kcal/mol, produces both Cl and Cl, whereas the minor (5%) channel, partitioning much less energy to relative kinetic energy, produces only ground spin-orbit state Cl atoms. The maximum internal energy of the radicals produced in the low-recoil-kinetic-energy channel is consistent with this channel producing electronically excited propargyl radicals. Finally, in contrast to previous studies, the present work determines the HCl recoil kinetic energy distribution and identifies the possible contribution to this spectrum from propargyl radicals cracking to C3+ ions in the mass spectrometer.     

Slice imaging and wave packet study of the photodissociation of CH3I in the blue edge of the A-band: evidence of reverse 3Q0 ← 1Q1 non-adiabatic dynamics

The photodissociation of CH(3)I in the blue edge (217-230 nm) of the A-band has been studied using a combination of slice imaging and resonance enhanced multiphoton ionization (REMPI) detection of the CH(3) fragment in the vibrational ground state (ν = 0). The profiles of the CH(3) (ν = 0) kinetic energy distributions and the photofragment anisotropies are interpreted in terms of the contribution of the excited surfaces involved in the photodissociation process, as well as the probability of non-adiabatic curve crossing between the (3)Q(0) and (1)Q(1) states. In the studied region, unlike in the central part of the A-band where absorption to the (3)Q(0) state dominates, the I((2)P(J)), with J = 1/2, 3/2, in correlation with CH(3) (ν = 0) kinetic energy distributions show clearly two contributions of different anisotropy, signature of the competing adiabatic and non-adiabatic dynamics, whose ratio strongly depends on the photolysis wavelength. The experimental results are compared with multisurface wave packet calculations carried out using the available ab initio potential energy surfaces, transition moments, and non-adiabatic couplings, employing a reduced dimensionality model. A good qualitative agreement is found between experiment and theory and both show evidence of reverse (3)Q(0)←(1)Q(1) non-adiabatic dynamics at the bluest excitation wavelengths both in the fragment kinetic energy and angular distributions.     

243～263nm CH3COCH3 的多光子电离研究

在243～263 nm紫外光波段通过质量选择光电离激发谱研究了丙酮（CH3COCH3）的光化学反应通道。分析母体离子CH3COCH3+和碎片离子CH3CO+ 、 CH3+的光电离激发谱和质谱峰宽可以知道: 此光波段丙酮分子的光化学反应主要包括了丙酮分子经由(S1,T1)中间态产生母体离子的（1+1）双光子电离通道,母体离子进一步解离产生碎片离子CH3+的“光电离-光解离”通道和丙酮分子经由(S1,T1)中间态解离成中性自由基碎片CH3CO后再进一步被双光子电离的“光解离-光电离”通道。由母体离子光电离激发谱双光子阈值波长（255.67 nm）给出的丙酮电离势（IP）为（9.696±0.004）eV。     

A computational study of the ground and excited state structure and absorption spectra of free-base N-confused porphine and free-base N-confused tetraphenylporphyrin

Computational investigations into the ground and singlet excited-state structures and the experimental ground-state absorption spectra of N-confused tetraphenylporphyrin tautomers 1e and 1i and N-confused porphines (NCP) 2e and 2i have been performed. Structural data for the ground state, performed at the B3LYP/6-31G(d), B3LYP/6-31+G(d)//B3LYP/6-31G(d), and B3LYP/6-311+G(d)//B3LYP/6-31G(d) levels, are consistent with those performed at lower levels of theory. Calculations of the gas-phase, ground-state absorption spectrum are qualitatively consistent with condensed phase experiments for predicting the relative intensities of the Q(0,0) and Soret bands. Inclusion of implicit solvation in the calculations substantially improves the correlation of the energy of the Soret band with experiment for both tautomers (1e, 435 nm predicted, 442 nm observed in DMAc; 1i, 435 nm predicted, 437 nm observed in CH2Cl2). The x- and y-polarized Q-band transitions were qualitatively reproduced for 1e in both the gas phase and with solvation, although the low-energy absorption band in 1i was predicted at substantially higher energy (646 nm in the gas phase and 655 nm with solvation) than observed experimentally (724 nm in CH2Cl2). Franck-Condon state and equilibrated singlet excited-state geometries were calculated for unsubstituted NCP tautomers 2e and 2i at the TD-B3LYP/SVP and TD-B3LYP/TZVP//TD-B3LYP/SVP levels. Electronic difference density plots were calculated from these geometries, thereby indicating the change of electron density in the singlet excited states. Adiabatic S1 and S2 geometries of these compounds were also calculated at the TD-B3LYP/SVP level, and the results indicate that while 2i is a more stable ground-state molecule by approximately 7.0 kcal mol-1, the energy difference for the S1 excited states is only approximately 1.0 kcal mol-1 and is 6.1 kcal mol-1 for the S2 excited states.     

Tunnelling under a conical intersection: application to the product vibrational state distributions in the UV photodissociation of phenols

When phenol is photoexcited to its S(1) (1(1)ππ?) state at wavelengths in the range 257.403 ≤ λ(phot) ≤ 275.133 nm the O-H bond dissociates to yield an H atom and a phenoxyl co-product, with the available energy shared between translation and well characterised product vibration. It is accepted that dissociation is enabled by transfer to an S(2) (1(1)πσ?) state, for which the potential energy surface (PES) is repulsive in the O-H stretch coordinate, R(O-H). This S(2) PES is cut by the S(1) PES near R(O-H) = 1.2 ? and by the S(0) ground state PES near R(O-H) = 2.1 ?, to give two conical intersections (CIs). These have each been invoked-both in theoretical studies and in the interpretation of experimental vibrational activity-but with considerable controversy. This paper revisits the dynamic mechanisms that underlie the photodissociation of phenol and substituted phenols in the light of symmetry restrictions arising from torsional tunnelling degeneracy, which has been neglected hitherto. This places tighter symmetry constraints on the dynamics around the two CIs. The non-rigid molecular symmetry group G(4) necessitates vibronic interactions by a(2) modes to enable coupling at the inner, higher energy (S(1)/S(2)) CI, or by b(1) modes at the outer, lower energy (S(2)/S(0)) CI. The experimental data following excitation through many vibronic levels of the S(1) state of phenol and substituted phenols demonstrate the effective role of the ν(16a) (a(2)) ring torsional mode in enabling O-H bond fission. This requires tunnelling under the S(1)/S(2) CI, with a hindering barrier of ～5000 cm(-1) and with the associated geometric phase effect. Quantum dynamic calculations using new ab initio PESs provide quantitative justification for this conclusion. The fates of other excited S(1) modes are also rationalised, revealing both spectator modes and intramolecular vibrational redistribution between modes. A common feature in many cases is the observation of an extended, odd-number only, progression in product mode ν(16a) (i.e., the parent mode which enables S(1)/S(2) tunnelling), which we explain as a Franck-Condon consequence of a major change in the active vibration frequency. These comprehensive results serve to confirm the hypothesis that O-H fission following excitation to the S(1) state involves tunnelling under the S(1)/S(2) CI-in accord with conclusions reached from a recent correlation of the excited state lifetimes of phenol (and many substituted phenols) with the corresponding vertical energy gaps between their S(1) and S(2) PESs.     

Photodissociation dynamics of acetoxime in gas phase

The dynamics of photodissociation of acetoxime at 193 nm, leading to the formation of (CH3)2C=N and OH fragments, has been investigated. The nascent OH radicals, which are both rotationally and vibrationally excited, were probed by laser photolysis-laser induced fluorescence technique. OH fragments in both v" = 1 and v" = 0 vibrational states were detected with a ratio of population in the higher to lower level of 0.07+/-0.01. The rotational temperatures of v" = 0 and 1 levels of OH radicals are 2650+/-150 K and 1290+/-20 K, respectively. More than 30% of the available energy, i.e., 115+/-21 kJ mol(-1) is partitioned into the relative translational energy of the fragments. The results of excited electronic state and transition state calculations at the configuration interaction with single electronic excitation level suggest that the dissociation takes place with an exit barrier of approximately 126 kJ mol(-1) at the triplet state (T2) potential energy surface, formed by internal conversions/intersystem crossing from the initially populated S2 state. Using the calculated transition state geometry and its energy, the observed energy distribution pattern can be reproduced by the hybrid model within experimental uncertainties. The presence of an exit barrier is further supported by the observation of N-OH dissociation upon 248 nm excitation, where the relative translational energy of the fragments is found to be approximately 96 kJ mol(-1). The photodissociation dynamics of acetoxime is compared with C-OH dissociation in enols and carboxylic acid and N-OH dissociation in nitrous acid. The observed emission (lambda(max)=430 nm) and the N-OH dissociation dynamics indicate crossing of the initially populated state to an emissive state of acetoxime, which is different from the dissociative state.     

Carbene formation in its lower singlet state from photoexcited 3H-diazirine or diazomethane. A combined CASPT2 and ab initio direct dynamics trajectory study

The potential energy surfaces of the ground and valence excited states of both 3H-diazirine and diazomethane have been studied computationally by mean of the CASSCF method in conjunction with the cc-pVTZ basis set. The energies of the critical points found on such surfaces have been recomputed at the CASPT2/cc-pVTZ level. Additionally, ab initio direct dynamic trajectory calculations have been carried out on the S(1) and S(2) surfaces, starting each trajectory run at the region dominated by the conformational molecular rearrangement of diazomethane. It is found that both isomers are interconnected along a C(s)() reaction coordinate on each potential surface. Radiationless deactivation of the corresponding S(1) state of each isomer occurs through the same point on the surface, an S(1)/S(0) conical intersection. Thereafter, the system has enough energy to surmount the barrier which leads to dissociation products (CH(2) + N(2)) on S(0) state. Therefore, photoexcitation to S(1) state of either diazirine of diazomethane produces methylene in its lower singlet state on a very short time scale (ca. 100 fs). Furthermore, both isomers can generate excited singlet carbene when they are excited onto the S(2) surface; in this case, they lose the activation energy passing through another common S(2)/S(1) conical intersection and then proceed to dissociation into carbene and N(2) on the S(1) surface. For the special case of methylene, it rapidly experiences deexcitation to S(0) state.     

A CASSCF/MR-CI study toward the understanding of wavelength-dependent and geometrically memorized photodissociation of formic acid

The S(0), T(1), and S(1) potential energy surfaces for the HCOOH dissociation and isomerization processes have been mapped with different ab initio methods. The wavelength-dependent mechanism for the HCOOH dissociation was elucidated through the computed potential energy surfaces and the surface crossing points. The HCOOH molecules in S(1) by excitation at 248 nm mainly decay to the ground state via the S(0) and S(1) vibronic interaction, followed by molecular eliminations in the ground state. The S(1) direct dissociation to HCO((2)A') + OH((2)Pi) is the dominant pathway upon photoexcitation at 240-210 nm. Meanwhile, there is a slight probability that the system relaxes to the ground state via the S(0) and S(1) vibronic interaction at these wavelengths. After irradiation of HCOOH at 193 nm, the S(1) direct dissociation into HCO((2)A') + OH((2)Pi) is energetically the most favorable pathway. In view of high IC efficiency at the S(0)/S(1) conical crossing, the S(1) --> S(0) internal conversion via the S(0)/S(1) point can occur with considerable efficiency. In addition, the S(1) isomerization probably plays a dominant role in the partially conformational memory of the HCOOH photodissociation, which has been discussed in detail.     

Insights into mechanistic photodissociation of acetyl chloride by ab initio calculations and molecular dynamics simulations

The potential energy surfaces of dissociation and elimination reactions for CH(3)COCl in the ground (S0) and first excited singlet (S1) states have been mapped with the different ab inito calculations. Mechanistic photodissociation of CH(3)COCl has been characterized through the intrinsic reaction coordinate and ab initio molecular dynamics calculations. The alpha-C-C bond cleavage along the S1 pathway leads to the fragments of COCl((2)A' ') and CH(3) ((2)A') in an excited electronic state and a high barrier exists on the pathway. This channel is inaccessible in energy upon photoexcitation of the CH(3)COCl molecules at 236 nm. The S1 alpha-C-Cl bond cleavage yields the Cl((2)P) and CH(3)CO(X(2)A') fragments in the ground state and there is very small or no barrier on the pathway. The S1 alpha-C-Cl bond cleavage proceeds in a time scale of picosecond in the gas phase, followed by CH(3)CO decomposition to CH(3) and CO. The barrier to the C-Cl bond cleavage on the S1 surface is significantly increased by effects of the argon matrix. The S1 alpha-C-Cl bond cleavage in the argon matrix becomes inaccessible in energy upon photoexcitation of CH(3)COCl at 266 nm. In this case, the excited CH(3)COCl(S1) molecules cannot undergo the C-Cl bond cleavage in a short period. The internal conversion from S1 to S0 becomes the dominant process for the CH(3)COCl(S1) molecules in the condensed phase. As a result, the direct HCl elimination in the ground state becomes the exclusive channel upon 266 nm photodissociation of CH(3)COCl in the argon matrix at 11 K.     

Photodissociation and multiphoton dissociative ionization processes in CH(3)S(2)CH(3) at 193 nm studied using velocity-map imaging

Dissociation and ionization processes in dimethyl disulfide, CH(3)S(2)CH(3), induced by one- or two-photon absorption of 193 nm light, have been studied using velocity-map ion imaging. The analysis of the ion images of the CH(3)S(2) (+), CH(3)S(+), S(2) (+), and S(+) fragments has allowed the characterization of the scattering dynamics of some of the main photolysis and dissociative-ionization processes. In particular, the experiments corroborate the formation of electronically excited SCH(3)((2)A(1)) products in the 193 nm photodissociation of dimethyl disulfide seen in earlier studies, and show that laser ionization provides a very sensitive method for their detection. The data have also allowed determination of the recoil energy and angular distributions of the CH(3)S(2) (+) and CH(3)S(+) products of the two-photon dissociative-ionization of the CH(3)S(2)CH(3) molecule. The measured distributions for these products are consistent with the formation of a transient parent ion which dissociates after a substantial intramolecular rearrangement, possibly yielding the most stable isomeric forms of the fragments, namely CH(2)S(2)H(+) and CH(2)SH(+).