Ab initio calculations employing the configuration interaction method including Davidson's corrections for quadruple excitations have been carried out to unravel the dissociation mechanism of acetylene dication in various electronic states and to elucidate ultrafast acetylene-vinylidene isomerization recently observed experimentally. Both in the ground triplet and the lowest singlet electronic states of C2H2(2+) the proton migration barrier is shown to remain high, in the range of 50 kcal/mol. On the other hand, the barrier in the excited 2 3A" and 1 3A' states decreases to about 15 and 34 kcal/mol, respectively, indicating that the ultrafast proton migration is possible in these states, especially, in 2 3A", even at relatively low available vibrational energies. Rice-Ramsperger-Kassel-Marcus calculations of individual reaction-rate constants and product branching ratios indicate that if C2H(2)2+ dissociates from the ground triplet state, the major reaction products should be CCH+(3Sigma-)+H+ followed by CH+(3Pi)+CH+(1Sigma+) and with a minor contribution (approximately 1%) of C2H+(2A1)+C+(2P). In the lowest singlet state, C2H+(2A1)+C+(2P) are the major dissociation products at low available energies when the other channels are closed, whereas at Eint>5 eV, the CCH+(1A')+H+ products have the largest branching ratio, up to 70% and higher, that of CH+(1Sigma+)+CH+(1Sigma+) is in the range of 25%-27%, and the yield of C2H++C+ is only 2%-3%. The calculated product branching ratios at Eint approximately 17 eV are in qualitative agreement with the available experimental data. The appearance thresholds calculated for the CCH++H+, CH++CH+, and C2H++C+ products are 34.25, 35.12, and 34.55 eV. The results of calculations in the presence of strong electric field show that the field can make the vinylidene isomer unstable and the proton elimination spontaneous, but is unlikely to significantly reduce the barrier for the acetylene-vinylidene isomerization and to render the acetylene configuration unstable or metastable with respect to proton migration.

The ab initio/Rice-Ramsperger-Kassel-Marcus (RRKM) approach has been applied to investigate the photodissociation mechanism of the azulene cation at different values of the photon energy. Reaction pathways leading to various decomposition products have been mapped out at the G3(MP2,CC)//B3LYP level and then the RRKM and microcanonical variational transition state theories have been applied to compute rate constants for individual reaction steps. Relative product yields (branching ratios) for the dissociation products have been calculated using the steady-state approach. The results show that a photoexcited azulene cation can readily isomerize to a naphthalene cation. The major dissociation channels are elimination of atomic hydrogen, an H2 molecule, and acetylene. The branching ratio of the H elimination channel decreases with an increase of the photon energy. The branching ratio of the acetylene elimination as well as that of the H2 elimination rise as the photon energy increases. The main C8H6+ fragment at all photon energies considered is a pentalene cation, and its yield decreases slightly with increasing excitation energy, whereas the branching ratios of the other C8H6+ fragments, phenylacetylene and benzocyclobutadiene cations, grow.

One of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10(-4)) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10(-7) at a high laser fluence and less than 10(-7) at a low laser fluence. Therefore, reexamining the possible contributions of thermally induced reactions in MALDI may be worthwhile. In this study, the concept of polar fluid was employed to explain the generation of primary ions in MALDI. A simple model, namely thermal proton transfer, was used to estimate the ion-to-neutral ratios in MALDI. We demonstrated that the theoretical calculations of ion-to-neutral ratios exhibit the same trend and similar orders of magnitude compared with those of experimental measurements. Although thermal proton transfer may not generate all of the ions observed in MALDI, the calculations demonstrated that thermally induced reactions play a crucial role in UV-MALDI.

Abstract. The ion-to-neutral ratios of four commonly used solid matrices, α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), sinapinic acid (SA), and ferulic acid (FA) in matrix-assisted laser desorption/ionization (MALDI) at 355 nm are reported. Ions are measured using a time-of-flight mass spectrometer combined with a time-sliced ion imaging detector. Neutrals are measured using a rotatable quadrupole mass spectrometer. The ion-to-neutral ratios of CHCA are three orders of magnitude larger than those of the other matrices at the same laser fluence. The ion-to-neutral ratios predicted using the thermal proton transfer model are similar to the experimental measurements, indicating that thermal proton transfer reactions play a major role in generating ions in ultraviolet-MALDI.

Photodissociation of pyridine, 2,6-d2-pyridine, and d5-pyridine at 193 and 248 nm was investigated separately using multimass ion imaging techniques. Six dissociation channels were observed at 193 nm, including C5NH5 --> C5NH4 + H (10%) and five ring opening dissociation channels, C5NH5 --> C4H4 + HCN, C5NH5 --> C3H3 + C2NH2, C5NH5 --> C2H4 +C3NH, C5NH5 --> C4NH2 + CH3 (14%), and C5NH5 --> C2H2 + C3NH3. Extensive H and D atom exchanges of 2,6-d2-pyridine prior to dissociation were observed. Photofragment translational energy distributions and dissociation rates indicate that dissociation occurs in the ground electronic state after internal conversion. The dissociation rate of pyridine excited by 248-nm photons was too slow to be measured, and the upper limit of the dissociation rate was estimated to be 2x10(3) s(-1). Comparisons with potential energies obtained from ab initio calculations and dissociation rates obtained from the Rice-Ramsperger-Kassel-Marcus theory have been made.