ALBERT

Notes: The energy partition in the products of ethylene photodissociation (including C2H4, C2D4, D2CCH2, cis- and trans-HDCCDH) at 193 and 157 nm and the rate constants of H loss channels were computed based on ab initio ethylene ground-state surfaces of which most were reported earlier. In the calculations of the energy partitions, a simple model was used in which the excess energy above the transition state is distributed statistically and the energy released by the exit barrier is described by the modified impulsive model. The rate constants of the ethylene H(D) elimination were calculated according to the variational RRKM (Rice–Ramsperger–Kassel–Marcus) theory, and the RRKM rate constants with tunneling corrections were obtained for vinyl decomposition at 193 nm. In contrast with previous conclusions drawn by LIF (laser induced fluorescence) studies, the rate constant calculations suggest that the H loss may be a nonstatistical process. However, the computed variational transition states for H loss appear reasonable as indicated by the translational energy. That with present investigation indicates that the atomic elimination proceeds via the predicted transition states though the process is nonstatistical. Analysis of the H2 translational energy measured at 193 and 157 nm by molecular beam experiments gives evidence that the overall mechanisms of the molecular elimination are different at the two wavelengths, which is also in disagreement with previous belief. At 193 nm, both H2 elimination channels may occur through the predicted transition states. On the other hand, further comparison of the theoretical and experimental translational energy of hydrogen molecule at 157 nm suggests that the observed (1,1E) reaction path is most likely of much higher "exit barrier" than the one computed. For the (1,2E) channel, the calculations are still in support of the computed transition state being the one along the experimentally observed pathway at 157 nm. © 1999 American Institute of Physics.

Notes: General expressions for internal conversion (IC) rate constant calculations have been derived by taking into account displacements, distortions, and rotation (mixing) of normal modes. The electronic part of the rate constant has been computed through the ab initio calculations of vibronic coupling. The corresponding expressions for the simplest two-mode case as well as for the general n-mode case have been derived. We demonstrate the effect of rotated (mixed) normal modes on the IC rate constants based on a model consisting of one promoting and two mixed modes. The dynamics of excited states of C2H4 has been investigated based on the internal conversion mechanism. The calculated rate of internal conversion show that the lifetimes of the excited π–3p and π–π* states of C2H4 are on the picosecond scale. We predict that if the molecule is excited to a Rydberg π–3p state, it relaxes to the ground state via the cascade mechanism, π–3p→π–3s(1B3u)→π–π*(1B1u)→1Ag. © 1998 American Institute of Physics.

Notes: In this article we report findings regarding various conical intersections between consecutive pairs of the five lowest 2A′ states of the C2H molecule. We found that conical intersections exist between each two consecutive 2A′ states. We showed that except for small (high-energy) regions in configuration space, the two lowest adiabatic states (i.e., the 1 2A′ and the 2 2A′) form a quasi-isolated system with respect to the higher states. We also revealed the existence of degenerate parabolical intersections, those with a topological (Berry) phase zero, formed by merging two conical intersections belonging to the 3 2A′ and the 4 2A′ states, and suggested a Jahn-Teller-type model to analyze them. Finally, we examined the possibility that the "frozen" locations of the carbons can be considered as points of conical intersection. We found that the relevant two-state topological phase is not zero nor a multiple of π, but that surrounding both carbons yields a zero topological phase. © 2001 American Institute of Physics.

Notes: The potential energy surface for the unimolecular decomposition of benzene and H+C6H5 recombination has been studied by the ab initio G2M(cc, MP2) method. The results show that besides direct emission of a hydrogen atom occurring without an exit channel barrier, the benzene molecule can undergo sequential 1,2-hydrogen shifts to o-, m-, and p-C6H6 and then lose a H atom with exit barriers of about 6 kcal/mol. o-C6H6 can eliminate a hydrogen molecule with a barrier of 121.4 kcal/mol relative to benzene. o- and m-C6H6 can also isomerize to acyclic isomers, ac-C6H6, with barriers of 110.7 and 100.6 kcal/mol, respectively, but in order to form m-C6H6 from benzene the system has to overcome a barrier of 108.6 kcal/mol for the 1,2-H migration from o-C6H6 to m-C6H6. The bimolecular H+C6H5 reaction is shown to be more complicated than the unimolecular fragmentation reaction due to the presence of various metathetical processes, such as H-atom disproportionation or addition to different sites of the ring. The addition to the radical site is barrierless, the additions to the o-, m-, and p-positions have entrance barriers of about 6 kcal/mol and the disproportionation channel leading to o-benzyne+H2 has a barrier of 7.6 kcal/mol. The Rice-Ramsperger-Kassel-Marcus and transition-state theory methods were used to compute the total and individual rate constants for various channels of the two title reactions under different temperature/pressure conditions. A fit of the calculated total rates for unimolecular benzene decomposition gives the expression 2.26×1014 exp(−53 300/T)s−1 for T=1000–3000 K and atmospheric pressure. This finding is significantly different from the recommended rate constant, 9.0×1015 exp(−54 060/T) s−1, obtained by kinetic modeling assuming only the H+C6H5 product channel. At T=1000 K, the branching ratios for the formation of H+C6H5 and ac-C6H6 are 29% and 71%, respectively. H+C6H5 becomes the major channel at T≥1200 K. The total rate for the bimolecular H+C6H5 reaction is predicted to be between 4.5×10−11 and 2.9×10−10cm3 molecule−1 s−1 for the broad range of temperatures (300–3000 K) and pressures (100 Torr–10 atm). The values in the T=1400–1700 K interval, ∼8×10−11 cm3 molecule−1 s−1, are ∼40% lower than the recommended value of 1.3×10−10 cm3 molecule−1 s−1. The recombination reaction leading to direct formation of benzene through H addition to the radical site is more important than H disproportionations at T〈2000 K. At higher temperatures the recombination channel leading to o-C6H4+H2 and the hydrogen disproportionation channel become more significant, so o-benzyne+H2 should be the major reaction channel at T〉2500 K. © 2001 American Institute of Physics.

Notes: In this Letter are presented and analyzed conical intersections which appear on the two symmetric sides of the C2v line of the C2H molecule. Two conical intersections (CI) of this kind, between the 3 2A′ and 4 2A′ electronic states, were found to be only a short distance apart, e.g., ∼0.3 Å for the CC distance of 1.25 Å. It is shown that these two CIs—to be termed CI twins—have opposite "charges" thus forming altogether a weak interaction. By increasing the CC distance, to 1.35 Å, the two twins coalesce to form a single CI. The interaction of this merged pair varies with the distance as q−1 (as is the case for conical intersections) but, in contrast to ordinary CIs, does not exhibit any topological effects and its intensity is shown to be zero. These features led us to term it as a degenerate CI or concisely DCI. © 2001 American Institute of Physics.

Notes: The three ab initio nonadiabatic coupling terms related to the three strongly coupled states of the C2H molecule, i.e., 2 2A′, 3 2A′, and 4 2A′, were studied applying the line integral technique [M. Baer, Chem. Phys. Lett. 35, 112 (1975)]. The following was verified: (1) Due to the close proximity of the conical intersections between these three states, two-state quantization cannot always be satisfied between two successive states. (2) It is shown that in those cases where the two-state quantization fails a three-state quantization is satisfied. This three-state quantization is achieved by applying the 3×3 nonadiabatic coupling matrix that contains the three relevant nonadiabatic coupling terms. The quantization is shown to be satisfied along four different contours (in positions and sizes) surrounding the relevant conical intersections. © 2002 American Institute of Physics.

Notes: Experimental and theoretical results are combined to show that vibrationally excited C2H radicals undergo photodissociation to produce C2 radicals mainly in the B 1Δg state. Infrared (IR) emissions from the photolysis of acetylene with a focused and unfocused 193 nm excimer laser have been investigated using step-scan Fourier transform infrared (FTIR) emission spectroscopy at both low and high resolution. With an unfocused laser, the low-resolution infrared emission spectra from the C2H radicals show a few new vibrational bands in addition to those previously reported. When the laser is focused, the only emissions observed in the 2800–5400 cm−1 region come from the electronic transitions of the C2 radicals. Most of the emissions are the result of the B 1Δg→A 1Πu transition of C2 although there are some contributions from the Ballik–Ramsay bands C2(b 3Σg−→a 3Πu). A ratio of [B 1Δg]/[b 3Σg−]=6.6 has been calculated from these results. High quality theoretical calculations have been carried out to determine what kind of ratio could be expected if the photodissociation products are formed solely by adiabatic dissociation from the excited states of C2H. To accomplish this, the geometries of different electronic states of C2H (X 2Σ+, A 2Π, 3–6 2A′, and 2–5 2A″) were optimized at the complete active space self consistent field [CASSCF(9,9)/6-311G**] level. The calculated normal modes and vibrational frequencies were then used to compute Franck–Condon factors for a variety of vibronic transitions. In order to estimate the oscillator strengths for transitions from different initial vibronic states of C2H, transition dipole moments were computed at different geometries. The overall Franck–Condon factor for a particular excited electronic state of C2H is defined as the sum of Franck–Condon factors originating from all the energetically accessible vibrational levels of C2H(X,A) states. The adiabatic excitation energies were calculated with the multi-reference configuration interaction/correlation-consistent polarized valence triple zeta [MRCI(9,9)/cc-PVTZ] method. The overall Franck–Condon factors were then multiplied by the corresponding oscillator strengths to obtain the total absorption intensities characterizing the probabilities for the formation of different excited states. Then, the excited states of C2H were adiabatically correlated to various electronic states of C2 (B 1Δg, A 1Πu, B′ 1Σg+, c 3Σu+, and b 3Σg−) to predict the photodissociation branching ratios from the different states of C2H, such as X(0,ν2,0), X(0,ν2,1), A(0,0,0), and A(0,1,0). For C2H produced by 193 nm photodissociation of acetylene, the calculations gave the following B:A:B′:b:c branching ratios of 38:32:10:14:6. This means that the theoretical branching ratio for the [B 1Δg]/[b 3Σg−] is 2.7, which is in excellent agreement with experiment. © 2001 American Institute of Physics.

Notes: Crossed molecular beam experiments were conducted to investigate the reaction of ground state carbon atoms, C(3Pj), with 1,2-butadiene, H2CCCH(CH3) (X 1A′), at three collision energies of 20.4 kJ mol−1, 37.9 kJ mol−1, and 48.6 kJ mol−1. Ab initio calculations together with our experimental data reveal that the reaction is initiated by a barrier-less addition of the carbon atom to the π system of the 1,2-butadiene molecule. Dominated by large impact parameters, C(3Pj) attacks preferentially the C2–C3 double bond to form i1 (mechanism 1); to a minor extent, small impact parameters lead to an addition of atomic carbon to the C1–C2 bond yielding i2 (mechanism 2). Both cyclic intermediates i1 and i2 ring open to triplet methylbutatriene complexes i3′ (H2CC*CCH(CH3)) and i3″, (H2CCC*CH(CH3)); C* denotes the attacked carbon atom. i3′ is suggested to decay nonstatistically prior to a complete energy randomization via atomic hydrogen loss forming 1- and 4-methylbutatrienyl CH3CCCCH2 (X 2A″) and HCCCCH(CH3) (X 2A″), respectively. The energy randomization in i3″ is likely to be complete. This isomer decomposes via H atom loss to 3-vinylpropargyl, H2CCCC2H3(X 2A″), as well as 1- and 4-methylbutatrienyl radicals. In high-density environments such as the inner regions of circumstellar envelopes of carbon stars and combustion flames, these linear C5H5 isomers might undergo collision induced isomerization to cyclic structures like the cyclopentadienyl radical. This isomer is strongly believed to be a key intermediate involved in the production of polycyclic aromatic hydrocarbon molecules and soot formation. These characteristics make the reactions of atomic carbon with C4H6 isomers compelling candidates to form C5H5 isomers in the outflow of AGB stars and oxygen-deficient hydrocarbon flames. © 2001 American Institute of Physics.