Atom Elimination Channel Research Articles

Atmospheric chemistry of (Z)- and (E)-1,2-dichloroethene: kinetics and mechanisms of the reactions with Cl atoms, OH radicals, and O3.

Smog chambers interfaced with in situ FT-IR detection were used to investigate the kinetics and mechanisms of the Cl atom, OH radical, and O3 initiated oxidation of (Z)- and (E)-1,2-dichloroethene (CHClCHCl) under atmospheric conditions. Relative and absolute rate methods were used to measure k(Cl + (Z)-CHClCHCl) = (8.80 ± 1.75) × 10-11, k(Cl + (E)-CHClCHCl) = (8.51 ± 1.69) × 10-11, k(OH + (Z)-CHClCHCl) = (2.02 ± 0.43) × 10-12, k(OH + (E)-CHClCHCl) = (1.94 ± 0.43) × 10-12, k(O3 + (Z)-CHClCHCl) = (4.50 ± 0.45) × 10-21, and k(O3 + (E)-CHClCHCl) = (1.02 ± 0.10) × 10-19 cm3 molecule-1 s-1 in 700 Torr of N2/air diluent at 298 ± 2 K. Pressure dependencies for the Cl atom reaction kinetics were observed for both isomers, consistent with isomerization occurring via Cl atom elimination from the chemically activated CHCl-CHCl-Cl adduct. The observed products from Cl initiated oxidation were HC(O)Cl (117-133%), CHCl2CHO (29-30%), and the corresponding CHClCHCl isomer (11-20%). OH radical initiated oxidation gives HC(O)Cl as a major product. For reaction of OH with (E)-CHClCHCl, (Z)-CHClCHCl was also observed as a product. A significant chlorine atom elimination channel was observed experimentally (HCl yield) and supported by computational results. Photochemical ozone creation potentials of 12 and 11 were estimated for (Z)- and (E)-CHClCHCl, respectively. Finally, an empirical kinetic relationship is explored for the addition of OH radicals or Cl atoms to small alkenes. The results are discussed in the context of the atmospheric chemistry of (Z)- and (E)-CHClCHCl.

VUV photodissociation of DNCO: dynamics of the D atom elimination channel

The D atom Rydberg tagging time-of-flight technique was applied to investigate the photodissociation dynamics of DNCO in the vacuum ultraviolet 133–137 nm region. The D atom product was detected and the corresponding product translational energy distributions and angular distributions were obtained. Three product channels, D + NCO(X2Π), D + NCO(A2Σ+) and D + NCO(B2Π), which arise from different dissociation pathways have been observed. It is found that the D + NCO(X2Π) channel involves two different dissociation pathways; one is via internal conversion from the excited state to the S0 state, and the other is via internal conversion from the excited state to the S1 state. The D + NCO(A2Σ+) channel was ascribed to be from dissociation on S2 surface, and the D + NCO(B2Π) channel possibly come from a relatively slow dissociation process. Vibrational structures observed in the D + NCO(A2Σ+) channel shows that there is dominant bending with a little stretching vibrational excitation of NCO(A2Σ+). This is consistent with what has been found in the previous study following VUV photodissociation of HNCO in a similar wavelength region.

Excited states dissociation dynamics of indole-x-carboxaldehyde (x = 4, 5, 6, 7): Theoretical and experimental study

Excited state dissociation dynamics of indole-x-carboxaldehyde (x = 4, 5, 6, 7) has been investigated by ab initio calculations and photodissociation in a molecular beam at 193 nm using multimass ion imaging techniques. It was found that dissociation processes strongly depends on the position of HCO functional group. Fast component of H atom elimination in the photofragment translational energy distribution suggesting that dissociation occurs in a repulsive excited state, is quite intense for all isomers excluding indole-7-carboxaldehyde, which H atom elimination channel is almost quenched. However, this is the only isomer having intramolecular hydrogen bonding between NH and HCO groups. Ab initio calculations of the excited states potential energy surfaces (PES) demonstrate that the additional low lying conical intersection between S1 and S0 states is expected for the isomer with intramolecular hydrogen bond, which provides fast radiationless relaxation into the S0 state without loss of the H atom.

Vacuum ultraviolet photodissociation dynamics of N2O via the C1Π state: The N(2Dj=5/2, 3/2) + NO(X2Π) product channels.

We study the vacuum ultraviolet photodissociation dynamics of N2O via the C1Π state by using the time-sliced velocity map ion imaging technique. Images of N(2Dj=5/2, 3/2) products from the N atom elimination channels were acquired at a set of photolysis wavelengths from 142.55 to 148.19 nm. Vibrational states of the NO(X2Π) co-fragments were partially resolved in experimental images. From these images, the product total kinetic energy release distributions (TKERs), branching ratios of the vibrational states of NO(X2Π) co-fragments, and the vibrational state specific angular anisotropy parameters (β) have been determined. Notable features were found in the experimental results: the TKERs show that the NO(X2Π) co-fragments are highly vibrationally excited. For the highly vibrationally excited state of NO(X2Π), a bimodal rotational structure is found at all the studied photolysis wavelengths. Furthermore, the vibrational state specific β values of both spin-orbit channels (j = 3/2, 5/2) clearly show a monotonic decrease as the vibrational quantum number of NO(X2Π) increases. These observations suggest that multiple dissociation pathways play a role in the formation of the N(2Dj=5/2, 3/2) + NO(X2Π) products: one corresponds to a fast dissociation pathway through the linear state (the C1Π state) following the initial excitation to a slightly bent geometry in the vicinity of the linear C1Π configuration, leading to the low rotationally excited components with relatively large β values; the other corresponds to a relatively slow dissociation pathway through the bent C(31A') or C(31A″) state, leading to moderately rotationally excited NO(X2Π) products with smaller β values.

Observation of H displacement and H2 elimination channels in the reaction of O(3P) with 1-butene from crossed beams and theoretical studies

We report preliminary combined experimental/theoretical results on O(3P)+1-butene reaction dynamics with focus on atomic hydrogen displacement and molecular hydrogen elimination channels. Dynamics and relative yield of the ethylvinoxy+H and ethylketene+H2 product channels are characterized in crossed beam experiments. Stationary points and energetics of triplet/singlet C4H8O potential energy surfaces (PESs) are calculated at CCSD(T)/CBS and CASPT2 level. O(3P) attack occurs on both unsaturated C-atoms with preference for the less substituted one leading, among other products, to C2H5CHCHO+H via an exit barrier on the triplet PES, and to C2H5CHCO+H2 via a very high exit barrier on the singlet PES following intersystem crossing.

Chlorine atom formation dynamics in the dissociation of halogenated pyridines after photoexcitation at 235 nm: A resonance enhanced multiphoton ionization-time of flight (REMPI-TOF) study

The photodissociation dynamics of halogen substituted pyridines, namely, 3-chloropyridine (ClPy) and 3-chloro-2,4,5,6-tetrafluoropyridine (ClFPy), has been studied around 235nm by detecting chlorine atoms in their spin orbit states Cl(2P3/2) and Cl∗(2P1/2) using the REMPI-TOF technique. We have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin–orbit branching ratio, for chlorine atom elimination channels. The TOF profiles for Cl and Cl∗ are found to be independent of laser polarization suggesting a zero value for β, within the experimental uncertainties. For 3-chloropyridine, the average translational energies for Cl and Cl∗ elimination channels are determined to be 3.7±1.0 and 7.0±1.5kcal/mol, respectively. Similarly, for 3-chloro-2,4,5,6-tetrafluoropyridine, the average translational energies for Cl and Cl∗ elimination channels are determined to be 8.0±1.5 and 9.0±1.5kcal/mol, respectively. The theoretical calculation suggests that the fluorine substitution increases the possibility of cross over to the π–σ∗ state from the initially prepared π–π∗ state.

Dynamics of Cl(2Pj) formation in the photodissociation of halogenated thiadiazole at 235 nm: A resonance enhanced multiphoton ionization-time of flight (REMPI-TOF) study

Abstract In one colour experiment, the photodissociation dynamics of halogen substituted thiadiazole, namely, 3,4-dichloro-1,2,5-thiadiazole, has been studied in a supersonic molecular beam around 235 nm, which prepares the molecules in its π–π* state. The study is conducted using resonance enhanced multiphoton ionization (REMPI) time-of-flight (TOF) technique, by detecting the nascent state of the primary chlorine atoms in their spin orbit states Cl(2P3/2) and Cl*(2P1/2). We have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin–orbit branching ratio, for chlorine atom elimination channels. State-specific TOF profiles are converted into kinetic energy distributions, using a least squares fitting method, taking into account the fragment anisotropies, βi. The TOF profiles for Cl and Cl* are found to be independent of laser polarization, i.e., the β is well characterized by a value of ∼0.0, within the experimental uncertainties. The translational energy distributions is well explained with only one component for both Cl and Cl* atom elimination channel. The average translational energies for Cl and Cl* channel are 5.2 ± 1.5 and 7.9 ± 1.5 kcal/mol, respectively. The energy partitioning into the translational modes is interpreted with the help of various models, such as impulsive and statistical models. The experimental studies revealing the nature of translational energies distribution for Cl and Cl* and its average value along with the theoretical calculations employing Time-Dependent Density Functional Theory (TD-DFT) and ab initio molecular orbital (MO) theory suggest that the initially prepared π–π* state crosses over to a nearby σ* repulsive state along the C Cl bond, from where the dissociation takes place. The results also indicates the role of fast internal conversion to ground state from the initially prepared π–π* state, from where various dissociation channels occurs. During the course of experiments, the absorption spectrum was also obtained with its absolute absorption cross section.

Ultrafast excited-state dynamics of 2,4-dimethylpyrrole.

The dynamics of photoexcited 2,4-dimethylpyrrole (DMP) were studied using time-resolved velocity map imaging spectroscopy over a range of photoexcitation wavelengths (276-238 nm). Two dominant H atom elimination channels were inferred from the time-resolved total kinetic energy release spectra, one which occurs with a time constant of ∼120 fs producing H atoms with high kinetic energies centered around 5000-7000 cm(-1) and a second channel with a time constant of ∼3.5 ps producing H atoms with low kinetic energies centered around 2500-3000 cm(-1). The first of these channels is attributed to direct excitation from the ground electronic state (S0) to the dissociative 1(1)πσ* state (S1) and subsequent N-H bond fission, moderated by a reaction barrier in the N-H stretch coordinate. In contrast to analogous measurements in pyrrole (Roberts et al. Faraday Discuss. 2013, 163, 95-116), the N-H dissociation times are invariant with photoexcitation wavelength, implying a relatively flatter potential in the vertical Franck-Condon region of the 1(1)πσ* state of DMP. The origins of the second channel are less clear-cut, but given the picosecond time constant for this process, we posit that this channel is indirect and is likely a consequence of populating higher-lying electronic states [e.g., 2(1)πσ* (S2)] which, following vibronic coupling into lower-lying intermediary states (namely, S1 or S0), leads to prompt N-H bond fission.

Reaction of Np atom with H₂O in the gas phase: reaction mechanisms and ab initio molecular dynamics study.

The gas-phase reaction of an Np atom with H2O was investigated using density functional theory and ab initio molecular dynamics. The reaction mechanisms and the corresponding potential energy profiles for different possible spin states were analyzed. Three reaction channels were found in the mechanism study: the isomerization channel, the H2 elimination channel, and the H atom elimination channel. The latter two were observed in the dynamics simulation. It was found that the branching ratio of the title reaction depends on the initial kinetic energy along the transition vector. Product energy distributions for the reaction were evaluated by performing direct classical trajectory calculations on the lowest sextet potential energy surface. The results indicate that most of the available energy appears as the translational energy of the products. The overall results indicate that the H2 elimination channel with low kinetic energy is thermodynamically favored but competes with the H atom elimination channel with higher kinetic energy.

Resonance enhanced multiphoton ionization time-of-flight (REMPI-TOF) study of tetrachloroethylene photodissociation at 235 nm: Role of bound [formula omitted] state

In one-color REMPI-TOF experiment, the photodissociation dynamics of tetrachloroethylene has been studied by probing the chlorine atom photofragments, namely, Cl (2P3/2) and Cl∗ (2P1/2), using 2+1 REMPI scheme in the 234–236nm region. We have determined the centre-of-mass photofragment speed distribution, recoil anisotropy parameter (β), and the spin–orbit branching ratio for chlorine atom elimination channels. The β is well characterized by a value of ∼0.0, within the experimental uncertainties. Two components, namely, the fast and the slow, are observed in the translational energy distributions of Cl and Cl∗. The average translational energies for the Cl and Cl∗ channels for the fast components are 17.6±1.9 and 14.0±1.7kcal/mol, while, that for the slow components are 2.2±1.0 and 3.2±1.0kcal/mol, respectively. To understand the nature of the dissociative potential energy surface involved in the chlorine atom formation channel, detailed theoretical calculations are performed using Time-dependent Density Functional Theory (TD-DFT) method.

Ab Initio Molecular Dynamics Study of the Reaction of U+ and U2+ with H2O in the Gas Phase: Direct Classical Trajectory Calculations

The gas phase reactions of U(+) and U(2+) with H2O were investigated using an ab initio molecular dynamics method. All of the information along the minimum energy path were calculated with density functional theory (DFT) and coupled cluster methods. For U(+) with H2O, the molecular dynamics simulations yield a branching ratio of 86% for the H2 elimination channel to 14% for the H atomic elimination channel in agreement with the quadruple ion trap mass spectrometry (QIT/MS) experimental ratio of 91% to 9%. In the case of U(2+) + H2O, there is a crossing of the potential energy surfaces (PES) after the first transition state. Crossing seams between the PES and possible spin inversion processes were studied by means of the intrinsic reaction coordinate (IRC) approach. For U(2+) with H2O, all trajectories are corresponds to H atom elimination channel, this is consistent with the Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) experimental results. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).

Effects of intramolecular hydrogen bonding on the excited state dynamics of phenol chromophores

The theoretical prediction and experimental confirmation of the 1πσ* excited state of phenol which is repulsive along the O-H bond has a large impact on the interpretation of phenol and tyrosine photochemistry. In this work, we demonstrate that this excited state changes significantly if the OH functional group is involved in the formation of an intramolecular hydrogen bond in the ground state. We investigate the excited state dynamics of 2-, 3-, and 4-hydroxyacetophenone (HAP) separately in a molecular beam at 193 nm using multimass ion imaging techniques. H atom elimination from the repulsive excited state and Norrish type I reactions are the major dissociation channels of 3-HAP and 4-HAP which do not have intramolecular hydrogen bonding. However, the H atom elimination channel is completely quenched for 2-HAP which shows intramolecular hydrogen bonding. In addition, the ground state and the excited state potential energy surfaces (PESs) of HAP, 2-hydroxybenzoyl fluoride, 2-hydroxybenzoyl chloride, and 2-hydroxybenzamide are investigated using ab initio calculations. The results also show that the excited state potential along the O-H bond distance of the hydroxyl group changes significantly for molecules with intramolecular hydrogen bonding. The changes include: (a) the repulsive potential energy surface becomes an attractive potential near the ground state equilibrium geometry, (b) the conical intersection between the first and the second excited states along the O-H bond moves to a much higher energy level, and (c) the conical intersection between the repulsive excited state and the ground state along the O-H bond distance disappears. The results suggest that the interpretation of the photochemistry for molecules with a phenol chromophore must take these effects into consideration.

Photodissociation Dynamics of Halogenated Thiophenes at 235 nm: A Resonance Enhanced Multiphoton Ionization-Time-of-Flight (REMPI-TOF) Study

The photodissociation dynamics of halogen-substituted thiophenes, namely, 2-chlorothiophene and 2-bromo-5-chlorothiophene, has been studied in a supersonic molecular beam around 235 nm, using resonance enhanced multiphoton ionization (REMPI) time-of-flight (TOF) technique, by detecting the nascent state of the primary halogen atoms. A single laser has been used for excitation of halothiophenes, as well as for the REMPI detection of photoproducts, namely, chlorine and bromine atoms, in their spin-orbit states X((2)P(3/2)) and X*((2)P(1/2)). We have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin-orbit branching ratio, for chlorine and bromine atom elimination channels. State-specific TOF profiles are converted into kinetic energy distributions, using a least-squares fitting method, taking into account the fragment anisotropies, β(ι). The TOF profiles for Cl, Cl*, Br, and Br* are found to be independent of laser polarization; i.e., the β is well characterized by a value of ~0.0, within the experimental uncertainties. For 2-chlorothiophene, we have observed two components for the Cl and only one component for the Cl* atom elimination channel in the translational energy distributions. The average translational energies for the fast and the slow components of the Cl channel are 3.0 ± 1.0 and 1.0 ± 0.5 kcal/mol, respectively. For Cl*, the average translational energy is 3.5 ± 1.0 kcal/mol. For 2-bromo-5-chlorothiophene, we have observed only one component for Cl, Cl*, Br, and Br* in the translational energy distributions. The average translational energies for the Cl and Cl* channels are 3.5 ± 1.0 and 5.0 ± 1.0 kcal/mol, respectively, whereas the average translational energies for the Br and Br* channels are 2.0 ± 1.0 and 3.5 ± 1.0 kcal/mol, respectively. The energy partitioning into the translational modes is interpreted with the help of various models, such as impulsive and statistical models. The ΔH(f)(298) value for 2-chlorothiophene has been estimated theoretically to be 23.5 kcal/mol.

Resonance enhanced multiphoton ionization time-of-flight (REMPI-TOF) study of phosphorous oxychloride (POCl3) dissociation at 235 nm: Dynamics of Cl(2Pj) formation

In one-color REMPI-TOF experiment, the photodissociation dynamics of POCl3 has been studied by photolyzing POCl3 and probing the chlorine atom photofragments, namely, Cl(2P3/2) and Cl∗(2P1/2) using 2+1 REMPI scheme, in the 234–236nm region. We have determined the centre-of-mass photofragment speed distribution, recoil anisotropy parameter, and the spin–orbit branching ratio for chlorine atom elimination channels. The anisotropy parameters for Cl and Cl∗ are the same, and characterized by a value of 0.0±0.05. Two components, namely, the fast and the slow, are observed in the translational energy distributions of Cl and Cl∗. The average translational energies for the Cl and Cl∗ channels for the fast components are 12.5±1.5 and 16.8±1.5kcal/mol, while, for the slow components, the average translational energies are 1.5±1.0 and 2.5±1.0kcal/mol, respectively. Apart from the chlorine atom elimination channel, Cl2 elimination is also observed in the photodissociation of POCl3.

Ultraviolet photodissociation dynamics of trichloroethylene at 235 nm

The photodissociation dynamics of trichloroethylene was investigated near 235 nm, (π,π*) transition, by detecting the nascent products, Cl (2P3/2) and Cl* (2P1/2), via 2 + 1 resonance enhanced multiphoton ionization. The photofragment speed distribution, the recoil anisotropy parameter β and the spin–orbit branching ratio for chlorine atom elimination channels were determined from time of flight profiles in polarization experiments. Based on the dynamical information, the features of potential energy surface along the reaction coordinate were discussed.

Dynamics of Cl (2Pj) Atom Formation in the Photodissociation of Fumaryl Chloride (ClCO − CH = CH − COCl) at 235 nm: A Resonance Enhanced Multiphoton Ionization (REMPI) Time-of-Flight (TOF) Study

The photodissociation dynamics of fumaryl chloride (ClCO-CH═CH-COCl) has been studied in a supersonic molecular beam around 235 nm using resonance enhanced multiphoton ionization (REMPI) time-of-flight (TOF) technique by detecting the nascent state of the primary chlorine atom. A single laser has been used for excitation of fumaryl chloride and the REMPI detection of chlorine atoms in their spin-orbit states, Cl ((2)P(3/2)) and Cl* ((2)P(1/2)). We have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin-orbit branching ratio for chlorine atom elimination channels. To obtain these, measured polarization-dependent and state-specific TOF profiles are converted into kinetic energy distributions, using a least-squares fitting method, taking into account the fragment recoil anisotropies, β(i). The TOF profiles for both Cl and Cl* are found to be independent of laser polarization; i.e., β is well characterized by a value of 0.0, within the experimental uncertainties. Two components, namely, the fast and the slow, are observed in the translational energy distribution, P(E(T)), of Cl and Cl* atoms, and assigned to be formed from different potential energy surfaces. The average translational energies for the fast components of the Cl and Cl* channels are 14.9 ± 1.6 and 16.8 ± 1.6 kcal/mol, respectively. Similarly, for the slow components, the average translational energies of the Cl and Cl* channels are 3.4 ± 0.8 and 3.1 ± 0.8 kcal/mol, respectively. The energy partitioning into the translational modes is interpreted with the help of various models, such as impulsive and statistical models. Apart from the chlorine atom elimination channel, molecular hydrogen chloride (HCl) elimination is also observed in the photodissociation process. The HCl product has been detected, using a REMPI scheme in the region of 236-237 nm. The observation of the molecular HCl in the dissociation process highlights the importance of the relaxation process, in which the initially excited parent molecule relaxes to the ground state from where the molecular (HCl) elimination takes place.

Photodissociation Dynamics of Phosphorus Trichloride (PCl3) at 235 nm Using Resonance Enhanced Multiphoton Ionization (REMPI) with Time-of-Flight (TOF) Mass Spectrometry

The photodissociation dynamics of phosphorus trichloride (PCl(3)) has been studied in a supersonic beam by resonance enhanced multiphoton ionization (REMPI), using time-of-flight (TOF) mass spectrometry. The study is focused on the nascent state of the primary chlorine atom, formed on excitation of the (n, sigma*) transition of the molecule around 235 nm. Dissociation of PCl(3) and the REMPI detection of chlorine atoms are performed, using the same laser around 235 nm. The photofragments, namely, Cl((2)P(3/2)) and Cl*((2)P(1/2)), are probed, using the 2+1 REMPI scheme in the 234-236 nm region. We have determined the photofragment speed distribution, the recoil anisotropy parameter beta, and the spin-orbit branching ratio for chlorine atom elimination channels. Polarization-dependent and state-specific TOF profiles are converted into kinetic energy distributions, using a least-squares fitting method, taking into account the fragment anisotropies. The anisotropy parameters for Cl and Cl* are characterized by values of 0.0 +/- 0.05 and 0.20 +/- 0.05, respectively. Two components, namely, the fast and the slow, are observed in the speed distribution (P(v)) of Cl and Cl* atoms, formed from different potential energy surfaces. The average translational energies for the Cl and Cl* channels for the fast component are 29.7 and 30.6 kcal/mol, respectively. Similarly, for the slow component, the average translational energies for the Cl and Cl* channels are 9.5 and 9.1 kcal/mol, respectively. The energy partitioning into the translational modes is interpreted with the help of an impulsive model, for the fast component, and a statistical model, for the slow component. Apart from the chlorine atom elimination channel, molecular chlorine (Cl(2)) elimination is also observed in the photodissociation of PCl(3). The observation of the molecular chlorine in the dissociation process and the bimodal translational energy distribution of the chlorine atom clearly indicate the existence of a crossover mechanism from the initially prepared state to the ground state.

Roaming Dynamics in Formaldehyde-d2 Dissociation

State-resolved photodissociation dynamics of formaldehyde-d(2), i.e., D(2)CO, at energies slightly above the deuterium atom elimination channel have been studied both experimentally and theoretically. The results showed a clear bimodal distribution of energy into molecular photofragments. Substantial translational excitation of products at high rotational levels of CO was observed together with the D(2) cofragment in moderately excited vibrational levels, whereas rather small translational energy release of CO in low rotational levels was matched by a large degree of vibrational excitation in the D(2) molecule. An analogous distribution of energy in two distinct channels has been recently observed under similar conditions in H(2)CO photolysis and attributed to two different dissociation pathways, namely, a pathway via the conventional transition state geometry and the previously unobserved pathway, deemed "roaming". Our experimental and theoretical data indicated that the same two dissociation pathways were responsible for the bimodal energy distribution into the molecular fragments resulting from the photolysis of D(2)CO. Energy partitioning into molecular products was compared between photolysis of H(2)CO and D(2)CO at energies slightly above the H/D atom abstraction threshold.

Photodissociation Dynamics of the Chromophores of the Amino Acid Tyrosine: p-Methylphenol, p-Ethylphenol, and p-(2-Aminoethyl)phenol

The photodissociation of p-methylphenol, p-ethylphenol, and p-(2-aminoethyl)phenol, chromophores of the amino acid tyrosine, was studied separately for each compound in a molecular beam at 248 nm using multimass ion imaging techniques. They show interesting side-chain size-dependent dissociation properties. Only one dissociation channel, that is, H atom elimination, was observed for both p-methylphenol and p-ethylphenol. The photofragment translational energy distributions and potential energy surfaces from ab initio calculation suggest that H atom elimination occurs from a repulsive excited state. On the other hand, the H atom elimination channel is quenched completely by internal conversion and/or intersystem crossing in p-(2-aminoethyl)phenol. Only C-C bond cleavage was observed from p-(2-aminoethyl)phenol. The photofragment translational energy distribution shows a slow component and a fast component. The fast component results from dissociation on an electronic excited state, but the slow component occurs only after the internal conversion to the ground electronic state. Comparison with the photodissociation of phenol and ethylbenzene is made.

Conformationally Controlled Chemistry: Excited-State Dynamics Dictate Ground-State Reaction

Ion imaging reveals distinct photodissociation dynamics for propanal cations initially prepared in either the cis or gauche conformation, even though these isomers differ only slightly in energy and face a small interconversion barrier. The product kinetic energy distributions for the hydrogen atom elimination channels are bimodal, and the two peaks are readily assigned to propanoyl cation or hydroxyallyl cation coproducts. Ab initio multiple spawning dynamical calculations suggest that distinct ultrafast dynamics in the excited state deposit each conformer in isolated regions of the ground-state potential energy surface, and, from these distinct regions, conformer interconversion does not effectively compete with dissociation.