Conformer specific dissociation dynamics of iodocyclohexane studied by velocity map imaging

The photodissociation dynamics of iodocyclohexane has been studied using velocity map imaging following excitation at many wavelengths within its A-band (230 ≤ λ ≤ 305 nm). This molecule exists in two conformations (axial and equatorial), and one aim of the present experiment was to explore the extent to which conformer-specific fragmentation dynamics could be distinguished. Ground (I) and spin-orbit excited (I?) state iodine atom products were monitored by 2 + 1 resonance enhanced multiphoton ionization, and total kinetic energy release (TKER) spectra and angular distributions derived from analysis of images recorded at all wavelengths studied. TKER spectra obtained at the longer excitation wavelengths show two distinct components, which can be attributed to the two conformers and the different ways in which these partition the excess energy upon C-I bond fission. Companion calculations based on a simple impulsive model suggest that dissociation of the equatorial (axial) conformer preferentially yields vibrationally (rotationally) excited cyclohexyl co-fragments. Both I and I? products are detected at the longest parent absorption wavelength (λ ～ 305 nm), and both sets of products show recoil anisotropy parameters, β > 1, implying prompt dissociation following excitation via a transition whose dipole moment is aligned parallel to the C-I bond. The quantum yield for forming I? products, Φ(I?), has been determined by time resolved infrared diode laser absorption methods to be 0.14 ± 0.02 (at λ = 248 nm) and 0.22 ± 0.05 (at λ = 266 nm). Electronic structure calculations indicate that the bulk of the A-band absorption is associated with transition to the 4A(') state, and that the (majority) I atom products arise via non-adiabatic transfer from the 4A(') potential energy surface (PES) via conical intersection(s) with one or more PESs correlating with ground state products.     

Matrix infrared spectroscopic and computational investigations of the lanthanide-methylene complexes CH2LnF2 with single Ln-C bonds

Laser-ablated lanthanide metal atoms were condensed with CH(2)F(2) in excess argon at 6 K or neon at 4 K. New infrared absorption bands are assigned to the oxidative addition product methylene lanthanide difluorides on the basis of deuterium substitution and vibrational frequency calculations with density functional theory (DFT). Two dominant absorptions in the 500 cm(-1) region are identified as lanthanide-fluoride stretching modes for this very strong infrared absorption. The predominantly lanthanide-carbon stretching modes follow a similar trend of increasing with metal size and have characteristic 30 cm(-1) deuterium and 14 cm(-1) (13)C isotopic shifts. The electronic structure calculations show that these CH(2)LnF(2) complexes are not analogous to the simple transition and actinide metal methylidenes with metal-carbon double bonds that have been investigated previously, because the lanthanide metals (in the +2 or +3 oxidation state) do not appear to form a π-type bond with the CH(2) group. The DFT and ab initio correlated molecular orbital theory calculations predict that these complexes exist as multiradicals, with a Ln-C σ bond and a single electron on C-2p weakly coupled with f(x) (x = 1 (Ce), 2 (Pr), 3(Nd), etc.) electrons in the adjacent Ln-4f orbitals. The Ln-C σ bond is composed of about 15% Ln-5d,6s and 85% C-sp(2) hybrid orbital. The Ln orbital has predominantly 6s and 5d character with more d-character for early lanthanides and increasing amounts of s-character across the row. The Ln-F bonds are almost purely ionic. Accordingly, the argon-neon matrix shifts are large (13-16 cm(-1)) for the ionic Ln-F bond stretching modes and small (～1 cm(-1)) for the more covalent Ln-C bond stretching modes.     

One-pot nitro-Mannich/hydroamination cascades for the direct synthesis of 2,5-disubstituted pyrroles using base and gold catalysis

An efficient, easy to perform, one-pot reaction cascade for the synthesis of 2,5-disubstituted pyrroles from p-toluenesulfonyl protected imines and 4-nitrobut-1-yne under a combination of base and gold(III) catalysis is reported.     

The E.S.R. spectrum of the tropolonyl radical

The many-body diagrammatic Rayleigh-Schrödinger perturbation theory (RSPT) is used for the calculation of ionization potentials of open-shell systems with one unpaired electron. This theoretical approach is tested on the simple examples of NO₂ and NF₂ molecules described by the INDO semi-empirical hamiltonian. The first- and second-order results are presented.     

ORION,minimizing reactive compensation on the electricity transmission system

This paper describes the need for a tool for reactive power planning and the consequent development of the program ORION. This program optimizes the cost of providing reactive compensation on the transmission network to ensure that voltage level requirements are met.     

Predissociation dynamics of Ã-state ammonia probed by two-photon excitation spectroscopy

Electronically excited ND₃(A¯) molecules have been prepared by laser two-photon excitation on theA¯¹A″₂—X¯¹′₁ transition and monitored via their resulting short-lived emission. The earlier observation of Douglas that ND₃(A¯) molecules carrying one quantum of out-of-plane bending vibration ν′₂ are least susceptible to predissociation, is confirmed. ND₃(A¯) predissociation rates are found to be both vibronic and rovibronic level dependent. Both observations may be understood by considering the likely form of the potential energy surface for ND₃(A¯) molecules in the region of the D₂N—D dissociation coordinate. At short D₂N—D separations this surface exhibits a barrier. The presence of a conical intersection (involving the ND₃ ground state surface) further out along the dissociation coordinate has a crucial influence on the magnitude of this barrier. The envisaged form of theA¯-state potential energy surface also provides a qualitative rationale for all previous experimental findings concerning electronic branching ratios and energy disposal amongst the primary photofragments arising in the photodissociation ofA¯-state ammonia.     

A new three-term conjugate gradient method

In this paper, we describe an implementation and give performance results for a conjugate gradient algorithm for unconstrained optimization. The algorithm is based upon the Nazareth three-term formula and incorporates Allwright preconditioning matrices and restart tests. The performance results for this combination compare favorably with existing codes.The support of the Science and Engineering Research Council is gratefully acknowledged.     

Monotonic subsequences in random sequences

The problems considered here deal with the distribution of the lengths of the longest monotonic subsequences in a sequence X₁, X₂,…, X_n of independent random variables with a common continuous distribution. It has been conjectured that with probability 1 the lengths of the longest ascending and longest descending subsequences are asymptotic to $\text{λn}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ as n → ∞ (for some constant λ). It is proved here that the probability that these lengths lie in the range ($\text{e}{}^{-1}\text{n}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{, en}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) tends to 1 as n → ∞. Furthermore considering the runs in X₁, X₂,…, X_n(the monotonic subsequences of consecutive terms) it is shown that with probability 1 the longest run up and longest run down will have lengths asymptotic to log n/log log n as n → ∞.