Christine J. Koh

Heats of Vaporization of Room Temperature Ionic Liquids by Tunable Vacuum Ultraviolet Photoionization

The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be DeltaH(vap)(298.15 K) = 195 +/- 19 kJ mol(-1). The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (DeltaH(vap)(298.15 K) = 174 +/- 12 kJ mol(-1)) and N-butyl-N-methylpyrrolidinium dicyanamide (DeltaH(vap)(298.15 K) = 171 +/- 12 kJ mol(-1)) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion pairs.

Tunable wavelength soft photoionization of ionic liquid vapors

Combined data of photoelectron spectra and photoionization efficiency curves in the near threshold ionization region of isolated ion pairs from [emim][Tf(2)N], [emim][Pf(2)N], and [dmpim][Tf(2)N] ionic liquid vapors reveal small shifts in the ionization energies of ion-pair systems due to cation and anion substitutions. Shifts toward higher binding energy following anion substitution are attributed to increased electronegativity of the anion itself, whereas shifts toward lower binding energies following cation substitution are attributed to an increase in the cation-anion distance that causes a lower Coulombic binding potential. The predominant ionization mechanism in the near threshold photon energy region is identified as dissociative ionization, involving the dissociation of the ion pair and the production of intact cations as the positively charged products.

Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with Cyano-Functionalized Anions

Because of the unusually high heats of vaporization of room-temperature ionic liquids (RTILs), volatilization of RTILs through thermal decomposition and vaporization of the decomposition products can be significant. Upon heating of cyano-functionalized anionic RTILs in vacuum, their gaseous products were detected experimentally via tunable vacuum ultraviolet photoionization mass spectrometry performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Experimental evidence for di- and trialkylimidazolium cations and cyano-functionalized anionic RTILs confirms thermal decomposition occurs primarily through two pathways: deprotonation of the cation by the anion and dealkylation of the imidazolium cation by the anion. Secondary reactions include possible cyclization of the cation and C2 substitution on the imidazolium, and their proposed reaction mechanisms are introduced here. Additional evidence supporting these mechanisms was obtained using thermal gravimetric analysis-mass spectrometry, gas chromatography-mass spectrometry, and temperature-jump infrared spectroscopy. In order to predict the overall thermal stability in these ionic liquids, the ability to accurately calculate both the basicity of the anions and their nucleophilicity in the ionic liquid is critical. Both gas phase and condensed phase (generic ionic liquid (GIL) model) density functional theory calculations support the decomposition mechanisms, and the GIL model could provide a highly accurate means to determine thermal stabilities for ionic liquids in general.

Simultaneous ion-pair photodissociation and dissociative ionization of an ionic liquid: velocity map imaging of vacuum-ultraviolet-excited 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Isolated gas-phase ionic liquid (IL) molecules, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N−]), are excited by laser-produced high-harmonic extreme ultraviolet light in the 17−26 eV range and the ions are probed by velocity map imaging. The velocities of the intact cation, Emim+, and intact anion, Tf2N−, are recorded in separate velocity map images. The kinetic energy distribution of the intact cation has both slow ions arising from previously reported dissociative ionization and fast ions from ion-pair dissociation of the neutral isolated ionic liquid (positive and negative ion pairs) where the branching ratio is approximately 0.18 ± 0.02:0.82 ± 0.02. The intact anion is also detected with a momentum that complements the higher velocity intact cation fragment, indicating that the process arises from two-body dissociation of the neutral ion-pair. Similar angular distributions for the anion and the higher velocity cation indicate that the electronic transition, which is above the ionization threshold and leads to ion-pair dissociation of the neutral, has a dipole moment perpendicular to the dissociating ion-pair bond. Observation of the ion-pair dissociation upon photoexcitation of the IL vapor not only reveals a previously unobserved photodissociation pathway for the ionic liquid, but it also provides direct evidence for the existence of the ion pairs in the isolated gas phase molecules.

Ultrafast decay of superexcited cΣu−4nlσgv=0,1 states of O2 probed with femtosecond photoelectron spectroscopy

Neutral superexcited states in molecular oxygen converging to the O(2)(+) c (4)Σ(u)(-) ion state are excited and probed with femtosecond time-resolved photoelectron spectroscopy to investigate predissociation and autoionization relaxation channels as the superexcited states decay. The c (4)Σ(u)(-) 4sσ(g) v=0, c (4)Σ(u)(-) 4sσ(g) v=1, and c (4)Σ(u)(-) 3dσ(g) v=1 superexcited states are prepared with pulsed high-harmonic radiation centered at 23.10 eV. A time-delayed 805 nm laser pulse is used to probe the excited molecular states and neutral atomic fragments by ionization; the ejected photoelectrons from these states are spectrally resolved with a velocity map imaging spectrometer. Three excited neutral O* atom products are identified in the photoelectron spectrum as 4d(1) (3)D(J)°, 4p(1) (5)P(J)° and 3d(1) (3)D(J)° fragments. Additionally, several features in the photoelectron spectrum are assigned to photoionization of the transiently populated superexcited states. Using principles of the ion core dissociation model, the atomic fragments measured are correlated with the molecular superexcited states from which they originate. The 4d(1) (3)D(J)° fragment is observed to be formed on a timescale of 65 ± 5 fs and is likely a photoproduct of the 4sσ(g) v = 1 state. The 4p(1) (5)P(J)° fragment is formed on a timescale of 427 ± 75 fs and correlated with the neutral predissociation of the 4sσ(g) v = 0 state. The timescales represent the sum of predissociation and autoionization decay rates for the respective superexcited state. The production of the 3d(1) (3)D(J)° fragment is not unambiguously resolved in time due to an overlapping decay of a v = 1 superexcited state photoelectron signal. The observed 65 fs timescale is in good agreement with previous experiments and theory on the predissociation lifetimes of the v = 1 ion state, suggesting that predissociation may dominate the decay dynamics from the v = 1 superexcited states. An unidentified molecular state is inferred by the detection of a long-lived depletion signal (reduction in autoionization) associated with the B (2)Σ(g)(-) ion state that persists up to time delays of 105 ps.