Trajectory approach to the mode-selected photodissociation of CS2

Through the study of photodissociation events in the CS(2) molecule that originate in various selected vibrational modes, but terminate in the same final predissociation state, we looked for the evidence that photodissociation processes can depend on the initial conditions. Such dependence would not occur within RRKM theory, because of its statistical assumptions. The experimental results were compared with trajectory calculations in normal mode coordinates, in which initial conditions were given in terms of coordinates and momenta. We have found that the photodissociation rate for events originating in the combination nu(1), nu(2) mode is higher than that for events from the pure nu(2) mode, and shows a large variation along the vibrational progression. The experimental observations agree with the trajectory calculations. In addition, the trajectory calculations predict that photodissociation events initiated at small values of the vibrational coordinates result in larger dissociation rates at low excess energy above the dissociation limit, while events from large values of the coordinates result in larger dissociation rates at high excess energies.     

Mode specific photodissociation of CS2(+) via the A2Π(u) state: a time-sliced velocity map imaging study

The vibrationally mediated photodissociation of CS(2)(+) cations via the A(2)Π(u)(ν(1),ν(2),0) state has been studied by means of the velocity map ion imaging technique. The measurements were made with a double resonance strategy. The CS(2)(+) cations were prepared by a (3 + 1) resonance enhanced multiphoton ionization method. The photo-fragment excitation spectrum of S(+) was recorded by scanning the photolysis laser via the A(2)Π(u)(ν(1),ν(2),0) state. By fixing the photolysis laser wavelength at the specific vibrational state, the (1 + 1) photodissociation images of S(+) photofragments from numerous vibrationally mediated states have been accumulated. The translational energy release spectra derived from the resulting images imply that the co-fragments, CS radicals, are both vibrationally and rotationally excited. The one-photon photodissociation without the vibrational state selection has also been performed. Comparing the vibrationally mediated photodissociation with one-photon photodissociation observations, clear evidence of vibrational state control of the photodissociation process is observed.     

Quantum Theory of ICN Photodissociation: Density Matrices of Photofragments from a Parallel Transition

A quantum treatment on ICN photodissociation from an initial parallel transition (Ω′ = 0 ← Ω″ = 0) to 1 the asymptote CN(|)+ I(²P_1/2) is presented. Density matrices of both photofragments are derived, and explicit expressions of the state multipoles in terms of the angular momentum coupling coefficients and the rotation‐bending factors have been obtained. The present theoretical framework provides a foundation to study photofragments with non‐null electronic and/or spin angular momenta. To investigate the angular momentum polarizations phenomena, these density matrices can play a prime role in laser‐based detections of state‐selected photofragments.     

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.     

Vector and scalar correlations in the photodissociation of NCCN

The CN photofragments from the photodissociation of NCCN at 193 nm have been measured by high-resolution transient absorption spectroscopy. Doppler-broadened profiles of isolated rotational lines in the 2-0 and 3–1 vibrational bands of the CN A---X transition were observed under collisionless conditions with a tunable, single-frequency Ti:sapphire ring laser. Analysis of the Dopple profiles reveals a vector correlation between the translation and rotation of CN photoproducts, with the angular momentum of the high rotational states increasingly perpendicular to the recoil velocity. After correction for vector correlations, the laboratory-frame scalar speed distribution of state-selected photoproducts can be determined. The mean squared laboratory velocity is directly related to the average internal energy of coincident CN fragments. The wings of the Doppler profiles indicate that the available energy for a pair of ground state CN photoproducts following 193 nm dissociation of NCCN at 295 K is 5300±150 cm⁻¹, which includes the average vibrational energy of the parent molecules selected by the photolysis laser. Phase space theory with an optimized available energy of 5300 cm⁻¹ produces laboratory speed distributions that are in qualitatively reasonable agreement with the kinetic energy measurements, but overestimate the total internal energy of the photofragments. The measurements are good enough to warrant comparison with more sophisticated models of unimolecular decomposition.     

Treatment of the K-quantum number in unimolecular reaction theory: insights from product correlations

The connection between the K-quantum number and product correlations in the barrierless unimolecular dissociation of symmetric-top molecules is explored to establish a qualitative diagnostic for the treatment of the K-rotor dynamics in unimolecular reaction theory. We find that fragment scalar and vector correlations can provide guidance in this matter, and the photodissociation dynamics of thermal NCNO to form CN and NO at several dissociation wavelengths are presented to demonstrate the utility of this approach. The "goodness" of the K-quantum number can be related to the amount of energy in the conserved vibrational modes at the inner transition state. On the basis of measured correlated vibrational distributions, the K-quantum number is found to be approximately conserved at the inner transition state for the photodissociation of NCNO at 514, 520, and 526 nm. The methodology, involving a comparison of product distributions from the photodissociation of jet and thermal ensembles at identical wavelengths, is general and may be applied to previously studied systems that dissociate along barrierless potential energy surfaces, CF(3)NO and CH(2)CO. In addition, vector correlations serve as a means to probe the K-mixing at the outer transition state, and measured v-j correlations in the photodissociation of thermal NCNO are presented.     

Mode-dependent enhancement of photodissociation and photoionization in a seven atom molecule

We report the first experimental demonstration of vibrational mode-dependent enhancement in photodissociation and photoionization of a seven atom molecule, methylamine (CH(3)NH(2)). The fundamental C-H stretches and the overtones or combinations of CH(3) bends were prepared via stimulated Raman excitation (SRE) prior to their 243.135 nm one-photon dissociation or two-photon ionization. The photodissociation or photoionization of the vibrationally excited molecules was achieved via 10 ns delayed or temporally overlapping SRE and UV pulses, respectively. It is shown that bending modes are more effective than stretches in promoting photodissociation and photoionization, since their UV excitation is favored by larger Franck Condon factors. This behavior provides clear evidence for vibrational mode-dependence in a relatively large molecule with a torsional degree of freedom, indicating that these modes survive intramolecular vibrational redistribution on a time scale considerably longer than hitherto inferred from previous studies.     

Vibrationally mediated photodissociation of ethene isotopic variants preexcited to the fourth C-H stretch overtone

H and D photofragments produced via vibrationally mediated photodissociation of jet-cooled normal ethene (C2H4), 1,2-trans-d2-ethene (HDCCDH), and 1,1-d2-ethene (CH2CD2), initially excited to the fourth C-H stretch overtone region, were studied for the first time. H and D vibrational action spectra and Doppler profiles were measured. The action spectra include partially resolved features due to rotational cooling, while the monitored room temperature photoacoustic spectra exhibit only a very broad feature in each species. Simulation of the spectral contours allowed determination of the band types and origins, limited precision rotational constants, and linewidths, providing time scales for energy redistribution. The H and D Doppler profiles correspond to low average translational energies and show slight preferential C-H over C-D bond cleavage in the deuterated variants. The propensities toward H photofragments emerge even though the energy flow out of the initially prepared C-H stretch is on a picosecond time scale and the photodissociation occurs following internal conversion, indicating a more effective release of the light H atoms.     

Intracluster stereochemistry in van der Waals complexes: steric effects in ultraviolet photodissociation of state-selected Ar-HOD/H2O

High-resolution IR-UV multiple resonance methods are employed to elucidate the photodissociation dynamics of quantum state-selected Ar-HOD and Ar-H(2)O van der Waals clusters. A single mode pulsed OPO operating in the region of the OH second overtone is used to prepare individual rovibrational states that are selectively photodissociated at specific excimer wavelengths. Subsequent fluorescence excitation of the resulting OH (OD) fragments yields dynamical information on the photofragmentation event and any resulting intracluster collisions. This technique is used to characterize spectroscopically the Pi(1(01)), nu(OH)=3<--Sigma(0(00)), v(OH)=0 overtone band of the Ar-HOD complex with an origin at 10648.27 cm(-1). The effects of Ar complexation on the dissociation dynamics are inferred by comparison of the OD photofragment quantum state distributions resulting from dissociation of single rovibrational states of the complex with those from isolated HOD photodissociation. The important role played by the initial internal state of the complex is demonstrated by comparison of the current Ar-HOD data with previously published results for the Ar-H(2)O Sigma(0(00))[03(-)> state. We interpret the dramatic differences in the dynamics of the two systems as manifestations of the nodal structure of the vibrational state in the parent complex and the way in which it governs the collision probability between the Ar atom and the escaping photofragments.     

Electronic angular momentum polarizations of photofragments: a case study of ICN photodissociation from a perpendicular transition

A quantum treatment on ICN photodissociation from an initial perpendicular transition (Omega'=+/-1<--Omega"=0) to the asymptote CN(|Sigma+,J'M'N'1/2>)+I(2P3/2) is presented. Density matrices of both photofragments are derived and explicit expressions of the state multipoles in terms of the angular momentum coupling coefficients and the rotation-bending factors have been obtained. To perceive the physical origin of electronic angular momentum polarizations of the iodine photofragments, a correlation scheme which considers the magnetic dipolar and the electrostatic dipole-quadrupole interactions between I and CN cofragments is proposed. For ICN precursors in the vibrational ground state or in the equally populated l-type split levels, the alignment parameters of the iodine photofragments in the molecular frame can be calculated according to this long-range interaction model. For the perpendicular transition |1Pi1><--|1Sigma0+>, its alignment parameters of I(2P3/2) from the incoherent and coherent transitions to the |Omega'=1> and |Omega'=-1> components are rho(0)2(1Pi1)=0.756 and rho2(2)(1Pi1)=-0.656, respectively. For the perpendicular transition to |3Pi1>, rho(0)2(3Pi1)=-0.878 and rho2(2)(3Pi1)=0.328 are from the incoherent transition, whereas rho(0)2(3Pi1)=0.122 and rho2(2)(3Pi1)=0.328 are from the coherent transition. To analyze the photoion images of iodine photofragments, angular distributions of I+ from the 2+1 resonance-enhanced multiphoton ionization detection scheme are derived.     

Time-resolved predissociation of the vibrationless level of the B state of CH3I

The predissociation dynamics of the vibrationless level of the first Rydberg 6s (B (1)E) state of CH(3)I has been studied by femtosecond-resolved velocity map imaging of both the CH(3) and I photofragments. The kinetic energy distributions of the two fragments have been recorded as a function of the pump-probe delay, and as a function of excitation within the umbrella and stretching vibrational modes of the CH(3) fragment. These observations are made by using (2 + 1) Resonant Enhanced MultiPhoton Ionization (REMPI) via the state of CH(3) to detect specific vibrational levels of CH(3). The vibrational branching fractions of the CH(3) are recovered by using the individual vibrationally state-selected CH(3) distributions to fit the kinetic energy distribution obtained by using nonresonant multiphoton ionization of either the I or the CH(3) fragment. The angular distributions and rise times of the two fragments differ significantly. These observations can be rationalized through a consideration of the alignment of the CH(3) fragment and the effect of this alignment on its detection efficiency. Two additional dissociation channels are detected: one associated with Rydberg states near 9.2 eV that were observed previously in photoelectron studies, and one associated with photodissociation of the parent cation around 15 eV.     

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.     

Evidence for new bands in the 3nu1 and 4nu1 regions of propyne

Vibrationally mediated photodissociation and room-temperature photoacoustic (PA) spectroscopy have been used for obtaining action (monitoring the yield of H photofragments) and absorption spectra of the second (3nu(1)) and third (4nu(1)) C-H acetylenic stretches overtone regions in propyne. The band contours appearing in these regions seem mostly regular even though they are perturbed, as expressed by the origin shifts in different K components, splitting of the K structure, and splitting due to resonances between neighboring states. Symmetric rotor simulations of the band contours of the PA and action spectra allowed extraction of the molecular parameters and rough estimates for the homogeneous broadening arising from energy flow to the bath vibrational states. We particularly benefited from the reduced congestion in the jet-cooled action spectra and their simulations, which enabled observation of yet unknown features in the vicinity of the 3nu(1) and 4nu(1) states. Particularly, the emergence of the new state in the 3nu(1) region was confirmed by the action spectra monitored at several differing jet temperatures, suggesting that it is a dark state in IR vibrational excitation that becomes brighter in UV excitation to the upper electronic state. The monitored and Gaussian-fitted Doppler profiles point to the release of H photofragments with low average translational energies, attributed to an indirect dissociation process occurring after internal conversion to the ground electronic state and isomerization to allene.     

Spectroscopy of highly excited vibrational states of HCN in its ground electronic state

An experimental technique based on a scheme of vibrationally mediated photodissociation has been developed and applied to the spectroscopic study of highly excited vibrational states in HCN, with energies between 29,000 and 30,000 cm(-1). The technique consists of four sequential steps: in the first one, a high power laser is used to vibrationally excite the sample to an intermediate state, typically (0,0,4), the nu3 mode being approximately equivalent to the C-H stretching vibration. Then a second laser is used to search for transitions between this intermediate state and highly vibrationally excited states. When one of these transitions is found, HCN molecules are transferred to a highly excited vibrational state. Third, a ultraviolet laser photodissociates the highly excited molecules to produce H and CN radicals in its A 2Pi electronic state. Finally, a fourth laser (probe) detects the presence of the CN(A) photofragments by means of an A-->B-->X laser induced fluorescence scheme. The spectra obtained with this technique, consisting of several rotationally resolved vibrational bands, have been analyzed. The positions and rotational parameters of the states observed are presented and compared with the results of a state-of-the-art variational calculation.     

State-to-state correlated study of CD3I photodissociation at 266 and 304 nm

High-resolution photofragment translational spectroscopy is used in this work to measure the translational and internal energy distributions in the CD3 and iodine fragments produced from the photodissociation of CD3I at 266 and 304 nm. Channel selected detection, via resonantly enhanced multiphoton ionization, combined with one-dimensional core sampling provides detailed information about vibrational state distributions of the CD3 fragments. The vibrational state distributions of CD3 fragments in the I*(2P12) channel have a propensity of nu2 ' umbrella bending mode with a maximum at nu2 ' = 1 for 266 nm photodissociation. For I*(2P12) channel at 304 nm photodissociation, vibrational state distributions of CD3 fragment have a maximum in the vibrational ground state. For the I(2P32) channel (1Q1 <-- 3Q(0+)), nu2 ' umbrella bending vibrational distribution is measured as the predominant vibrational mode but has a much broader distribution when compared to that of the I* channel. The vibrational state distributions of the CD3 fragment produced from the perpendicular transition, i.e., 3Q1, which was determined at 304 nm photodissociation, has a maximum at nu2 ' = 1. The curve crossing possibility between the 1Q1 and 3Q(0+) adiabatic potentials is determined as 0.19 for 266 and 0.85 for 304 nm. The trend in reaction dynamics in 266 and 304 nm photodissociation of CD3I is compared with theoretical calculations. A bond dissociation energy D0(C-I) = 56.60+/-0.5 kcal/mol was derived by applying laws of energy conservation.     

Atomic polarization in the photodissociation of diatomic molecules

The angular momentum polarization of atomic photofragments provides a detailed insight into the dynamics of the photodissociation process. In this article, the origins of electronic angular momentum polarization are introduced and experimental and theoretical methods for the measurement or calculation of atomic orientation and alignment parameters described. Many diatomic photodissociation systems are surveyed, in order to provide an overview both of the historical development of the field and of the most state-of-the-art contemporary studies.     

Vibrational overtone spectra of N-H stretches and intramolecular dynamics on the ground and electronically excited states of methylamine

The vibrational pattern and energy flow in the N-H stretch manifolds and the dissociation dynamics of methylamine (CH(3)NH(2)) were investigated via vibrationally mediated photodissociation. Action spectra and Doppler profiles, reflecting the yield of the ensuing H photofragments, versus near infrared/visible vibrational excitation and UV excitation, respectively, were measured. The jet-cooled action spectra and the simultaneously measured room temperature photoacoustic spectra of the first to third N-H stretching overtones exhibit broad features, somewhat narrower in the former, consisting of barely recognized multiple bands. Two phases of fitting of the spectroscopic data were performed. In the first phase, the raw data were analyzed to obtain band positions, types, intensities, and transition linewidths. In the second, the information derived from the first phase was then used as data in a fit to joint local mode/normal mode (LM/NM) and NM Hamiltonian parameters. The derived parameters predicted well band positions and allowed band assignment. The LM/NM Hamiltonian and the extracted Lorentzian linewidths enabled the determination of the initial pathways for energy redistribution and the overall temporal behavior of the N-H stretch and doorway states, as a result of Fermi couplings and interactions with bath states. The results indicate a nonstatistical energy flow in the V=2 manifold region, pointing to the dependence of the coupling on specific low order resonances rather than on the total density of bath states. The Doppler profiles suggest lower average translational energies for the released H photofragments, in particular, for V=3 and 4 as compared to V=1 and 2, implying a change in the mechanism for bond cleavage.     

Design of an infrared laser pulse to control the multiphoton dissociation of the Fe-CO bond in CO-heme compounds

Optimal control theory is used to design a laser pulse for the multiphoton dissociation of the Fe-CO bond in the CO-heme compounds. The study uses a hexacoordinated iron-porphyrin-imidazole-CO complex in its ground electronic state as a model for CO liganded to the heme group. The potential energy and dipole moment surfaces for the interaction of the CO ligand with the heme group are calculated using density functional theory. Optimal control theory, combined with a time-dependent quantum dynamical treatment of the laser-molecule interaction, is then used to design a laser pulse capable of efficiently dissociating the CO-heme complex model. The genetic algorithm method is used within the mathematical framework of optimal control theory to perform the optimization process. This method provides good control over the parameters of the laser pulse, allowing optimized pulses with simple time and frequency structures to be designed. The dependence of photodissociation yield on the choice of initial vibrational state and of initial laser field parameters is also investigated. The current work uses a reduced dimensionality model in which only the Fe-C and C-O stretching coordinates are explicitly taken into account in the time-dependent quantum dynamical calculations. The limitations arising from this are discussed in Sec. IV.     

Theory of the photodissociation of ozone in the Hartley continuum; effect of vibrational excitation and O(1D) atom velocity distribution

The effect of vibrational excitation on the photodissociation cross section of ozone in the Hartley continuum is examined. The calculations make use of newly computed potential energy and transition dipole moment surfaces. The initial vibrational states of the ozone are computed using grid based techniques and the first few ab initio computed vibrational energy level spacings agree to within 10 cm(-1) with experimental values. The computed total absorption cross sections arising from different initial vibrational states of ozone are discussed in the light of the nature of the transition dipole moment surface. The computed cross section for excitation from the ground vibrational-rotational state is in good agreement with the experimentally measured cross section. Excitation of the asymmetric stretching vibration of ozone has a marked effect on both the form and magnitude of the photodissociation cross section. The velocity distributions of highly reactive O(1D) atoms arising from the photodissociation process in different wavelength ranges is also presented. The results show that the O(1D) atoms travel with a most probable translational velocity of 2.030 km s(-1) corresponding to a translational energy of 0.342 eV or 33.0 kJ mol(-1).     

Photodissociation of acryloyl chloride in the gas phase

The 193 nm photodissociation dynamics of CH2 CHCOCl in the gas phase has been examined with the technique of time-resolved Fourier transform infrared emission (TR-FTIR) spectroscopy.Vibrationally excited photofragments of CO (≤ 5),HCl (≤ 6),and C2H2 were observed and two photodissociation channels,the C-Cl fission channel and the HCl elimination channel have been identified.The vibrational and rotational state distributions of the photofragments CO and HCl have been acquired by analyzing their fully rotationally resolved v→v-1 rovibrational progressions in the emission spectra,from which it has been firmly established that the mechanism involves production of HCl via the four-center molecular elimination of CH2 CHCOCl after its internal conversion from the S1 state to the S0 state.In addition to the dominant C-Cl bond fission along the excited S1 state,the S1→S0 internal conversion has also been found to play an important role in the gas phase photolysis of CH2 CHCOCl as manifested by the considerable yield of HCl.