A recent review (Ashfold et al., Phys. Chem. Chem. Phys., 2010, 12, 1218) highlighted the important role of dissociative excited states formed by electron promotion to σ* orbitals in establishing the photochemistry of many molecular hydrides. Here we extend such considerations to molecular halides, with a particular focus on iodobenzene. Two experimental techniques (velocity mapped ion imaging (VMI) and time resolved infrared (IR) diode laser absorption) and electronic structure calculations have been employed in a comprehensive study of the near ultraviolet (UV) photodissociation of gas phase iodobenzene molecules. The VMI studies yield the speeds and angular distributions of the I((2)P(3/2)) and I*((2)P(1/2)) photofragments formed by photolysis in the wavelength range 330 ≥λ≥ 206 nm. Four distinct dissociation channels are observed for the I((2)P(3/2)) atom products, and a further three channels for the I*((2)P(1/2)) fragments. The phenyl (Ph) radical partners formed via one particular I* product channel following excitation at wavelengths 305 ≥λ≥ 250 nm are distributed over a sufficiently select sub-set of vibrational (v) states that the images allow resolution of specific I* + Ph(v) channels, identification of the active product mode (ν(10), an in-plane ring breathing mode), and a refined determination of D(0)(Ph-I) = 23,390 ± 50 cm(-1). The time-resolved IR absorption studies allow determination of the spin-orbit branching ratio in the iodine atom products formed at λ = 248 nm (ϕ(I*) = [I*]/([I] + [I*]) = 0.28 ± 0.04) and at 266 nm (ϕ(I*) = 0.32 ± 0.05). The complementary high-level, spin-orbit resolved ab initio calculations of sections (along the C-I bond coordinate) through the ground and first 19 excited state potential energy surfaces (PESs) reveal numerous excited states in the energy range of current interest. Except at the very shortest wavelength, however, all of the observed I and I* products display limiting or near limiting parallel recoil anisotropy. This encourages discussion of the fragmentation dynamics in terms of excitation to states of A(1) total symmetry and dissociation on the 2A(1) and 4A(1) (σ* ← n/π) PESs to yield, respectively, I and I* products, or via non-adiabatic coupling to other σ* ← n/π PESs that correlate to these respective limits. Similarities (and differences) with the available UV photochemical data for the other aryl halides, and with the simpler (and more thoroughly studied) iodides HI and CH(3)I, are summarised.

The UV photochemistry of various fluorinated iodobenzenes (4-fluoro-, 2,4-difluoro-, 3,5-difluoro-, and perfluoro-iodobenzene) has been investigated at many wavelengths by velocity map imaging, time-resolved near infrared absorption spectroscopy and (spin-orbit resolved) ab initio calculations of the ground and excited state potentials along the C-I stretch coordinate, R(C-I). The textbook description of the near UV photochemistry of CH(3)I, i.e., σ∗←n excitation to the (3)Q(0+) state, followed by direct dissociation (to yield spin-orbit excited iodine atom (I∗) products) or by non-adiabatic coupling via a conical intersection (CI) with the (1)Q(1) potential (to yield ground state iodine (I) atoms) is shown to provide a good zero-order model for aryl iodide photochemistry also. However, the aryl halides also possess occupied π and low-lying π∗ orbitals, and have lower (C(2v) or C(s)) symmetry than CH(3)I. Both of these factors introduce additional subtleties. For example, excitations to and predissociation of ππ∗ excited states provide additional routes to I products, most obviously at long UV wavelengths. nσ∗∕πσ∗ configuration mixing stabilizes the (analogue of the) (3)Q(0+) potential energy surface (PES), to an extent that scales with the degree of fluorination; the corresponding 4A(1) PES in C(6)F(5)I is actually predicted to exhibit a minimum at extended R(C-I). This has the effect of extending the long wavelength threshold for forming I∗ products. The lowered symmetry enables an additional (sloped) CI with the 5A(2) (9A(") in 2,4-difluorobenzene) PES, which provides an extra non-adiabatic route to (fast) ground state I atoms when populating the 4A(1) PES at shorter UV excitation wavelengths.

Absolute peak absorption cross sections and pressure broadening coefficients have been recorded with sub-Doppler limited instrumental resolution for selected rotational lines in the 2(0)(2)4(0)(1) vibronic band of the formaldehyde A(1)A2-X(1)A1 electronic transition. The measured absorption cross sections range between (0.18 +/- 0.01) and (10.1 +/- 0.08) x 10(-19) cm2 molecule(-1) and are considerably larger than values from the literature recorded using apparatus where instrumental broadening was significant. However, comparisons with spectral simulations with equivalent resolution from Smith et al. (J. Phys. Chem. A 2006, 110, 11645-11653) are in excellent agreement. Pressure broadening was studied for the collision partners CH2O, CO2, N2, O2, Ne, Kr, Ar, and He, and the resulting broadening coefficients were found to be reduced in comparison to equivalent values measured in infrared regions, consistent with the reduced dipole moment of the upper state probed in this work. Cavity-enhanced absorption spectroscopy (CEAS) measurements were undertaken using calibrated low concentration (2.9-4.6 ppmv) samples from a permeation source and demonstrate a noise equivalent absorption of 1.2 x 10(-6) cm(-1) Hz(-1/2). This implies a minimum detectable formaldehyde concentration with the current system in atmospheric air of 172 ppbv Hz(-1/2).