Temperature Dependence of Desorbed Ions and Neutrals and Ionization Mechanism of Matrix-Assisted Laser Desorption/Ionization.

Two separate temperature-dependent experiments were performed to investigate the ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) of matrix 2,5-dihydroxybenzoic acid (2,5-DHB). First, the angular resolved intensity and velocity distributions of neutrals desorbed from the 2,5-DHB solid sample through UV laser (355 nm) pulse irradiation were measured using a rotating quadrupole mass spectrometer. Second, the desorbed neutrals, at an angle normal to the surface, and the desorbed ions were simultaneously detected for each laser shot using the quadrupole mass spectrometer and a time-of-flight mass spectrometer, respectively. Both experiments were conducted at two initial temperatures: 100 and 300 K. The measurements from these two experiments were used to calculate the initial temperature dependence of the ion-to-neutral ratio. The results closely agreed with the predictions of the temperature-dependent ion-to-neutral ratio using the thermal model, indicating that thermally induced proton transfer is the dominant reaction that generates initial ions of 2,5-DHB in UV-MALDI.

Dynamics Insight into Isomerization and Dissociation of Hot Criegee Intermediate CH3CHOO.

We study the isomerization and dissociation of syn-CH3CHOO with high internal energies by combining electronic structure calculations, ab initio molecular dynamics, and RRKM microcanonical variational transition-state theories. The results show a striking effect of the internal energy on the reaction fate of syn-CH3CHOO. With lower internal energies, syn-CH3CHOO prefers isomerizing to vinyl hydroperoxide, which then produces hydroxyl radical. As the available internal energy increases, the O-elimination channel becomes more competitive and eventually the dominant channel. A third channel leading to methyl dioxirane is found to be less competitive than the former two. However, this channel is highly exothermic and produces greenhouse gases CH4 and CO2; thus, further investigation is needed to quantify its potential impact on the atmosphere. The present study provides new insight on clarifying the unimolecular reaction fate of hot syn-CH3CHOO and theoretical solutions for revealing the impact of internal energy on the complex gas phase reactions.

Ion-to-Neutral Ratios and Thermal Proton Transfer in Matrix-Assisted Laser Desorption/Ionization.

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.

Ion intensity and thermal proton transfer in ultraviolet matrix-assisted laser desorption/ionization.

The ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) was investigated by measuring the total cation intensity (not including sodiated and potasiated ions) as a function of analyte concentration (arginine, histidine, and glycine) in a matrix of 2,4,6-trihydroxyacetophenone (THAP). The total ion intensity increased up to 55 times near the laser fluence threshold as the arginine concentration increased from 0% to 1%. The increases were small for histidine, and a minimal increase occurred for glycine. Time-resolved fluorescence intensity was employed to investigate how analytes affected the energy pooling of the matrix. No detectable energy pooling was observed for pure THAP and THAP/analyte mixtures. The results can be described by using a thermal proton transfer model, which suggested that thermally induced proton transfer is crucial in the primary ion generation in UV-MALDI.

Does decarboxylation make 2,5-dihydroxybenzoic acid special in matrix-assisted laser desorption/ionization?

RATIONALE: Among the six positional isomers of dihydroxybenzoic acid (DHB), 2,5-DHB is a more favorable matrix for use in matrix-assisted laser desorption/ionization (MALDI) than the other isomers because of its high ion-generation efficiency at 337 and 355 nm. The generation of hydroquinone or p-benzoquinone through the decarboxylation of 2,5-DHB has been suggested to play a crucial role in the ion-generation efficiency of 2,5-DHB. METHODS: The mass spectra of desorbed neutrals generated from MALDI were measured using electron impact ionization (70 eV) and a quadrupole mass spectrometer and vacuum ultraviolet (118 nm) photoionization and a time-of-flight mass spectrometer. The mass spectra of desorbed ions generated from MALDI were investigated using a time-of-flight mass spectrometer. The dissociation barrier height and dissociation rate of decarboxylation were calculated by an ab initio method and RRKM theory. RESULTS: Decarboxylation of neutral 2,5-DHB and 2,5-DHB cations was not observed. Theoretical calculations indicated that decarboxylation of neutral 2,5-DHB and 2,5-DHB cations is too slow to occur. CONCLUSIONS: The high ion-generation efficiency of the 2,5-DHB matrix at 337 and 355 nm is not related to decarboxylation.

Thermal proton transfer reactions in ultraviolet matrix-assisted laser desorption/ionization.

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.

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 methoxybenzoic acid at 193 nm.

The theoretical prediction and experimental confirmation of the 1πσ* repulsive excited state along O-H bond of phenol have large impact on the interpretation of phenol and tyrosine photochemistry. In this work, we investigated the photodissociation dynamics of 2-, 3-, and 4-methoxybenzoic acid (MOBA) in a molecular beam at 193 nm using multimass ion imaging techniques. In addition, the ground state and the excited state potential energy surfaces of MOBA were investigated using ab initio calculations, and branching ratios were predicted by Rice-Ramsperger-Kassel-Marcus theory. The results show that (1) the excited state potential of 1πσ* along O-CH(3) bond remains similar to that of phenol and anisole, (2) CH(3) elimination is the major channel for three MOBA isomers, and (3) photofragment translational energy distributions show bimodal distributions, representing the dissociation on the ground state and repulsive excited state, respectively. Comparison to the study of hydroxbenzoic acid [Y. L. Yang, Y. A. Dyakov, Y. T. Lee, C. K. Ni, Y. L. Sun, and W. P. Hu, J. Chem. Phys. 134, 034314 (2011)] shows that only the intramolecular hydrogen bonding has significant effects on the excited state dynamics of phenol chromophores.

Photodissociation dynamics of benzyl alcohol at 193 nm.

Photodissociation dynamics of benzyl alcohol, C(6)H(5)CH(2)OH and C(6)H(5)CD(2)OH, in a molecular beam was investigated at 193 nm using multimass ion imaging techniques. Four dissociation channels were observed, including OH elimination and H(2)O elimination from the ground electronic state, H atom elimination (from OH functional group), and CH(2)OH elimination from the triplet state. The dissociation rate on the ground state was found to be 7.7 × 10(6) s(-1). Comparison to the potential energy surfaces from ab initio calculations, dissociation rate, and branching ratio from Rice-Ramsperger-Kassel-Marcus calculations were made.

Energy transfer of highly vibrationally excited naphthalene: collisions with CHF3, CF4, and Kr.

Energy transfer of highly vibrationally excited naphthalene in the triplet state in collisions with CHF(3), CF(4), and Kr was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. Highly vibrationally excited naphthalene (2.0 eV vibrational energy) was formed via the rapid intersystem crossing of naphthalene initially excited to the S(2) state by 266 nm photons. The shapes of the collisional energy-transfer probability density functions were measured directly from the scattering results of highly vibrationally excited naphthalene. In comparison to Kr atoms, the energy transfer in collisions between CHF(3) and naphthalene shows more forward scatterings, larger cross section for vibrational to translational (V → T) energy transfer, smaller cross section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation, especially in the range -ΔE(d) = -100 to -800 cm(-1). On the other hand, the difference of energy transfer properties between collisional partners Kr and CF(4) is small. The enhancement of the V → T energy transfer in collisions with CHF(3) is attributed to the large attractive interaction between naphthalene and CHF(3) (1-3 kcal/mol).

Alkylation effects on the energy transfer of highly vibrationally excited naphthalene.

The energy transfer of highly vibrationally excited isomers of dimethylnaphthalene and 2-ethylnaphthalene in collisions with krypton were investigated using crossed molecular beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques at a collision energy of approximately 300 cm(-1). Angular-resolved energy-transfer distribution functions were obtained directly from the images of inelastic scattering. The results show that alkyl-substituted naphthalenes transfer more vibrational energy to translational energy than unsubstituted naphthalene. Alkylation enhances the V→T energy transfer in the range -ΔE(d)=-100~-1500 cm(-1) by approximately a factor of 2. However, the maximum values of V→T energy transfer for alkyl-substituted naphthalenes are about 1500~2000 cm(-1), which is similar to that of naphthalene. The lack of rotation-like wide-angle motion of the aromatic ring and no enhancement in very large V→T energy transfer, like supercollisions, indicates that very large V→T energy transfer requires special vibrational motions. This transfer cannot be achieved by the low-frequency vibrational motions of alkyl groups.

Energy transfer of highly vibrationally excited phenanthrene and diphenylacetylene.

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold phenanthrene and diphenylacetylene in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer between naphthalene and Kr, energy transfer between phenanthrene and Kr shows a larger cross-section for vibrational to translational (V → T) energy transfer, a smaller cross-section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation. These differences are further enlarged in the comparison between naphthalene and diphenylacetylene. In addition, less complex formation and significant increases in the large V → T energy transfer probabilities, termed supercollisions in diphenylacetylene and Kr collisions were observed. The differences in the energy transfer between these highly vibrationally excited molecules are attributed to the low-frequency vibrational modes, especially those vibrations with rotation-like wide-angle motions.

Photodissociation dynamics of hydroxybenzoic acids.

Aromatic amino acids have large UV absorption cross-sections and low fluorescence quantum yields. Ultrafast internal conversion, which transforms electronic excitation energy to vibrational energy, was assumed to account for the photostability of amino acids. Recent theoretical and experimental investigations suggested that low fluorescence quantum yields of phenol (chromophore of tyrosine) are due to the dissociation from a repulsive excited state. Radicals generated from dissociation may undergo undesired reactions. It contradicts the observed photostability of amino acids. In this work, we explored the photodissociation dynamics of the tyrosine chromophores, 2-, 3- and 4-hydroxybenzoic acid in a molecular beam at 193 nm using multimass ion imaging techniques. We demonstrated that dissociation from the excited state is effectively quenched for the conformers of hydroxybenzoic acids with intramolecular hydrogen bonding. Ab initio calculations show that the excited state and the ground state potential energy surfaces change significantly for the conformers with intramolecular hydrogen bonding. It shows the importance of intramolecular hydrogen bond in the excited state dynamics and provides an alternative molecular mechanism for the photostability of aromatic amino acids upon irradiation of ultraviolet photons.

Energy transfer of highly vibrationally excited biphenyl.

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold biphenyl in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer of naphthalene, energy transfer of biphenyl shows more forward scattering, less complex formation, larger cross section for vibrational to translational (V→T) energy transfer, smaller cross section for translational to vibrational and rotational (T→VR) energy transfer, larger total collisional cross section, and more energy transferred from vibration to translation. Significant increase in the large V→T energy transfer probabilities, termed supercollisions, was observed. The difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally cold biphenyl is very similar to the difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally hot naphthalene. The low-frequency vibrational modes with out-of-plane motion and rotationlike wide-angle motion are attributed to make the energy transfer of biphenyl different from that of naphthalene.

Photodissociation dynamics of tryptophan and the implication of asymmetric photolysis.

Photodissociation of amino acid tryptophan in a molecular beam at wavelengths of 212.8 and 193 nm, corresponding to excitation to the second and third absorption bands, was investigated using multimass ion imaging techniques. The respective wavelengths also represent excitation to the edge of a positive circular dichroism band and the center of a negative circular dichroism band of L-tryptophan. Only one dissociation channel was observed at both photolysis wavelengths: C(8)NH(6)CH(2)CHNH(2)COOH-->C(8)NH(6)CH(2)+CHNH(2)COOH. Dissociation rates were found to be 1.3x10(6) and 5x10(6) s(-1) at the respective wavelengths. Comparison to theoretical calculation indicates that dissociation occurs on the ground state after internal conversion. Implication of asymmetric photolysis is discussed.

Photodissociation dynamics of benzoic acid.

The photodissociation of benzoic acid at 193 and 248 nm was investigated using multimass ion imaging techniques. Three dissociation channels were observed at 193 nm: (1) C(6)H(5)COOH-->C(6)H(5)+COOH, (2) C(6)H(5)COOH-->C(6)H(5)CO+OH, and (3) C(6)H(5)COOH-->C(6)H(6)+CO(2). Only channels, (2) and (3), were observed at 248 nm. Comparisons of the ion intensities and photofragment translational energy distributions with the potential energies obtained from ab initio calculations and the branching ratios obtained from the Rice-Ramsperger-Kassel-Marcus theory suggest that the dissociation occurs on many electronic states.

Photodissociation and photoionization of 2,5-dihydroxybenzoic acid at 193 and 355 nm.

Photodissociation and photoionization of 2,5-dihydroxybenzoic acid (25DHBA), at 193 and 355 nm were investigated separately in a molecular beam using multimass ion imaging techniques. Two channels competed after excitation by one 193 nm photon. One channel is dissociation from the repulsive excited state along O-H bond distance, resulting in H atom elimination from meta-OH functional group. The other channel is internal conversion to the ground state, followed by H(2)O elimination. Some of the fragments further proceeded to secondary dissociation. On the other hand, absorption of one 355 nm photon gave rise to H(2)O elimination channel on the ground state. Absorption of more than one 355 nm photon resulted in the three-body dissociation which also occurs on the ground state. Dissociation on the excited state does not play a role at 355 nm. The large concentration ratio (2×10(5)), between neutral fragments and cations produced from 355 nm multiphoton excitation indicates that internal conversion followed by dissociation, is the major channel for 355 nm multiphoton excitation. Multiphoton ionization is a minor channel. Multiphoton ionization of 25DHBA clusters only produces 25DHBA cations. Neither anion nor protonated 25DHBA cation were observed. It is very different from the ions produced from solid matrix-assisted laser desorption/ionization (MALDI), experiments. This suggests that protonated 25DHBA and negatively charged 25DHBA generated in MALDI experiments does not simply result from the ionization following proton transfer reactions or charge transfer reactions of the clusters in the gas phase.

355 nm multiphoton dissociation and ionization of 2, 5-dihydroxyacetophenone.

Multiphoton dissociation and ionization of 2,5-dihydroxyacetophenone (DHAP), an important matrix compound in UV matrix-assisted laser desorption/ionization (MALDI), is studied in a molecular beam at 355 nm using multimass ion imaging mass spectrometer and time-of-flight mass spectrometry. For laser fluence larger than 130 mJ/cm(2), nearly all of the irradiated molecules absorb at least one photon. The absorption cross section was found to be sigma = 1.3(+/-0.2) x 10(-17)cm(2). Molecules excited by two photons quickly dissociate into fragments. The major channels are (1) C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2)CO + CH(3) and (2) C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2) + COCH(3). Molecules absorbing three or more photons become parent ions or crack into smaller ionic fragments. The concentration ratio of ions (parent ions and ionic fragments) to neutral fragments is about 10(-6):1. Changing the molecular beam carrier gas from He at 250 Torr to Ar at 300 Torr results in molecular beam clustering (dimers and trimers). Multiphoton ionization of clusters by a 355 nm laser beam produces only dimer cations, (C(6)H(3)(OH)(2)COCH(3))(2)(+). Protonated clusters or negatively charged ions, observed from a solid sample of DHAP using 355 nm multiphoton ionization, were not found in the molecular beam. The experimental results indicate that the photoionization occurs in the gas phase after DHAP vaporizes from the solid phase may not play an important role in the MALDI process.

Photodissociation dynamics of 2,5-dihydroxyacetophenone.

Photodissociation of 2,5-dihydroxyacetophenone (DHAP), an important matrix compound in matrix-assisted laser desorption/ionization (MALDI), was studied in a molecular beam at 193 nm using multimass ion imaging techniques. Two major dissociation channels were observed, including (1) C(6)H(3)(OH)(2)COCH(3) --> OC(6)H(3)(OH)COCH(3) + H and (2) C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2) + COCH(3). The minor channels include C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2)CO + CH(3) and/or C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2) + CO + CH(3). The photofragment translational energy distribution suggests that reaction 1 occurs at an excited state in which the potential along the O-H bond distance is repulsive. Comparison to the branching ratios from RRKM calculations suggests that reaction 2 does not occur at either the ground state or the triplet state or that if it does occur at one of these states it must not follow the RRKM model. A comparison to the photodissociation dynamics of acetophenone and phenol and its derivatives was made.

Photodissociation dynamics of small aromatic molecules studied by multimass ion imaging.

The photodissociation dynamics of various aromatic molecules, studied using multimass ion imaging techniques, is reviewed. The experimental data reveals new isomerization and dissociation mechanisms. Our investigation of benzene, pyridine, and pyrimidine finds that H-atom elimination thresholds remain the same for the three molecules. We also notice that ring-opening dissociation thresholds decrease rapidly with the increase of the number of nitrogen atoms in the aromatic ring. Hydrogen atom elimination is the sole dissociation channel for benzene at 193 nm. Along with H-atom elimination, we observe five distinct ring-opening dissociation channels for pyridine at 193 nm. No dissociation channels were observed for benzene and pyridine at 248 nm. Ring-opening dissociation channels are the major channels for pyrimidine, which dissociates at 193 nm and also at 248 nm. A six-membered to seven-membered ring isomerization was observed for photodissociation processes involving toluene, m-xylene, aniline, 4-methylpyridine, alpha-fluorotoluene, and 4-fluorotoluene, indicating a general isomerization mechanism for all such aromatic molecules. What is significant, is that during the isomerization, atoms (i.e., carbon, nitrogen, fluorine, and hydrogen) belonging to respective alkyl or amino groups are involved in an exchange with atoms within the aromatic ring. This type of isomerization is not observed in other aromatic isomerization mechanisms. For small tyrosine chromophores, such as phenol, 4-methylphenol, and 4-ethylphenol, H-atom elimination from a repulsive excited state plays a key role. However, dissociation is quenched in large chromophores like 4-(2-aminoethyl)-phenol. Our work demonstrates the capability and high sensitivity of multimass ion imaging techniques in the study of aromatic compounds.