Alan Heays

Source of Nitrogen Isotope Anomaly in HCN in the Atmosphere of Titan

The ^(14)N/^(15)N ratio for N_2 in the atmosphere of Titan was recently measured to be a factor of 2 higher than the corresponding ratio for HCN. Using a one-dimensional photochemical model with transport, we incorporate new isotopic photoabsorption and photodissociation cross sections of N_2, computed quantum-mechanically, and show that the difference in the ratio of ^(14)N/^(15)N between N_2 and HCN can be explained primarily by the photolytic fractionation of ^(14)N^(14)N and ^(14)N ^(15)N. The [HC^(14)N]/[HC^(15)N] ratio produced by N_2 photolysis alone is 23. This value, together with the observed ratio, constrains the flux of atomic nitrogen input from the top of the atmosphere to be in the range (1-2) × 10^9 atoms cm^(-2) s^(-1).

Isotope selective photodissociation of N2 by the interstellar radiation field and cosmic rays

Photodissociation of 14N2 and 14N15N occurs in interstellar clouds, circumstellar envelopes, protoplanetary discs, and other environments due to UV radiation from stellar sources and the presence of cosmic rays. This source of N atoms initiates the formation of complex N-bearing species and influences their isotopic composition. To study the photodissociation rates of 14N15N by UV continuum radiation and both isotopologues in a field of cosmic ray induced photons. To determine the effect of these on the isotopic composition of more complex molecules. High-resolution photodissociation cross sections of N2 are used from an accurate and comprehensive quantum- mechanical model of the molecule based on laboratory experiments. A similarly high-resolution spectrum of H2 emission following interactions with cosmic rays has been constructed. The spectroscopic data are used to calculate dissociation rates which are input into isotopically differentiated chemical models, describing an interstellar cloud and a protoplanetary disc. The dissociation rate of 14N15N in a Draine field assuming 30K excitation is 1.73x10-10s-1 and the rate due to cosmic rays assuming an H2 ionisation rate of 10-16s-1 is about 10-15s-1, with up to a factor of 10 difference between isotopologues. Shielding functions for 14N15N by 14N2, H2, and H are presented. Incorporating these into an interstellar cloud model, an enhancement of the atomic 15N/14N ratio is obtained due to the self-shielding of external radiation at an extinction of about 1.5 mag. This effect is larger where grain growth has reduced the opacity of dust to ultraviolet radiation. The transfer of photolytic isotopic fractionation N2 to other molecules is significant in a disc model, and is species dependent with 15N enhancement approaching a factor of 10 for HCN.

High resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

The first comprehensive high-resolution photoabsorption spectrum of (14)N(15)N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet and span 100 000-109 000 cm(-1) (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N(2) that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schrödinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.

High-Resolution Oscillator Strength Measurements of the v' = 0,1 Bands of the B-X, C- X, and E-X Systems in Five Isotopologues of Carbon Monoxide

We report oscillator strengths for six strong vibrational bands between 105.0 and 115.2 nm, associated with transitions from the v = 0 level of the X 1Σ+ ground state to the v = 0 and 1 levels of the B 1Σ+, C 1Σ+, and E 1Π states, in 12C16O, 12C17O, 12C18O, 13C16O, and 13C18O. These measurements extend the development of a comprehensive database of line positions, oscillator strengths, and linewidths of photodissociating transitions for all astrophysically relevant CO isotopologues. The E-X bands, in particular, play central roles in CO photodissociation and fractionation models of interstellar clouds and circumstellar disks including the early solar nebula. The resolving powers of the room-temperature measurements, R = 300,000-400,000, allow for the analysis of individual line strengths within bands; the measurements reveal J-dependences in the branch intensities of the C(v = 0,1)-X(0) and E(v = 0,1)-X(0) bands in all isotopologues. Minimal or no isotopologue dependence was found in the f-values of the C(v = 0,1)-X(0) and E(v = 0,1)-X(0) bands at a ~5% uncertainty level. Revised dissociation branching ratios for the C(v = 0,1) and E(v = 0,1) levels are computed based on these f-values. The weak isotopologue dependence of the f-values presented here eliminates this mechanism as an explanation for the large 17O enrichments seen in recent laboratory photolysis experiments on CO at wavelengths from 105 to 108 nm.

Photodissociation and photoionisation of atoms and molecules of astrophysical interest

A new collection of photodissociation and photoionisation cross sections for 102 atoms and molecules of astrochemical interest has been assembled, along with a brief review of the basic processes involved. These have been used to calculate dissociation and ionisation rates, with uncertainties, in a standard ultraviolet interstellar radiation field (ISRF) and wavelength-dependent radiation fields. The new ISRF rates generally agree within 30% with our previous compilations, with a few notable exceptions. The reduction of rates in shielded regions was calculated as a function of dust, molecular and atomic hydrogen, atomic C, and self-shielding column densities. The relative importance of shielding types depends on the species in question and the dust optical properties. The new data are publicly available from the Leiden photodissociation and ionisation database. Sensitivity of rates to variation of temperature and isotope, and cross section uncertainties, are tested. Tests were conducted with an interstellar-cloud chemical model, and find general agreement (within a factor of two) with the previous iteration of the Leiden database for the ISRF, and order-of-magnitude variations assuming various kinds of stellar radiation. The newly parameterised dust-shielding factors makes a factor-of-two difference to many atomic and molecular abundances relative to parameters currently in the UDfA and KIDA astrochemical reaction databases. The newly-calculated cosmic-ray induced photodissociation and ionisation rates differ from current standard values up to a factor of 5. Under high temperature and cosmic-ray-flux conditions the new rates alter the equilibrium abundances of abundant dark cloud abundances by up to a factor of two. The partial cross sections for H2O and NH3 photodissociation forming OH, O, NH2 and NH are also evaluated and lead to radiation-field-dependent branching ratios.

Photodissociation and chemistry of N2 in the circumstellar envelope of carbon-rich AGB stars

Context. The envelopes of asymptotic giant branch (AGB) stars are irradiated externally by ultraviolet photons; hence, the chemistry is sensitive to the photodissociation of N2 and CO, which are major reservoirs of nitrogen and carbon, respectively. The photodissociation of N2 has recently been quantified by laboratory and theoretical studies. Improvements have also been made for CO photodissociation. Aims. For the first time, we use accurate N2 and CO photodissociation rates and shielding functions in a model of the circumstellar envelope of the carbon-rich AGB star, IRC +10216. Methods. We use a state-of-the-art chemical model of an AGB envelope, the latest CO and N2 photodissociation data, and a new method for implementing molecular shielding functions in full spherical geometry with isotropic incident radiation. We compare computed column densities and radial distributions of molecules with observations. Results. The transition of N2→ N (also, CO → C → C+) is shifted towards the outer envelope relative to previous models. This leads to different column densities and radial distributions of N-bearing species, especially those species whose formation/destruction processes largely depend on the availability of atomic or molecular nitrogen, for example, CnN (n = 1, 3, 5), CnN− (n = 1, 3, 5), HCnN (n = 1, 3, 5, 7, 9), H2CN and CH2CN. Conclusions. The chemistry of many species is directly or indirectly affected by the photodissociation of N2 and CO, especially in the outer shell of AGB stars where photodissociation is important. Thus, it is important to include N2 and CO shielding in astrochemical models of AGB envelopes and other irradiated environments. In general, while differences remain between our model of IRC +10216 and the observed molecular column densities, better agreement is found between the calculated and observed radii of peak abundance.

Chemistry and Distribution of Daughter Species in the Circumstellar Envelopes of O-Rich AGB Stars

Context. Thanks to the advent of Herschel and ALMA, new high-quality observations of molecules present in the circumstellar envelopes of asymptotic giant branch (AGB) stars are being reported that reveal large differences from the existing chemical models. New molecular data and more comprehensive models of the chemistry in circumstellar envelopes are now available. Aims. The aims are to determine and study the important formation and destruction pathways in the envelopes of O-rich AGB stars and to provide more reliable predictions of abundances, column densities, and radial distributions for potentially detectable species with physical conditions applicable to the envelope surrounding IK Tau. Methods. We use a large gas-phase chemical model of an AGB envelope including the effects of CO and N 2 self-shielding in a spherical geometry and a newly compiled list of inner-circumstellar envelope parent species derived from detailed modeling and observations. We trace the dominant chemistry in the expanding envelope and investigate the chemistry as a probe for the physics of the AGB phase by studying variations of abundances with mass-loss rates and expansion velocities. Results. We find a pattern of daughter molecules forming from the photodissociation products of parent species with contributions from ion-neutral abstraction and dissociative recombination. The chemistry in the outer zones differs from that in traditional PDRs in that photoionization of daughter species plays a significant role. With the proper treatment of self-shielding, the N → N 2 and C + → CO transitions are shifted outward by factors of 7 and 2, respectively, compared with earlier models. An upper limit on the abundance of CH 4 as a parent species of (≲2.5 × 10 -6 with respect to H 2 ) is found for IK Tau, and several potentially observable molecules with relatively simple chemical links to other parent species are determined. The assumed stellar mass-loss rate, in particular, has an impact on the calculated abundances of cations and the peak-abundance radius of both cations and neutrals: as the mass-loss rate increases, the peak abundance of cations generally decreases and the peak-abundance radius of all species moves outwards. The effects of varying the envelope expansion velocity and cosmic-ray ionization rate are not as significant. Conclusions.

Structure and predissociation of the 3p sigma D-u (3)Sigma(+)(u) Rydberg state of N2: First extreme-ultraviolet and new near-infrared observations, with coupled-channels analysis

The 3psigma(u)D (3)Sigma(u) (+) Rydberg state of N(2) is studied experimentally using two high-resolution spectroscopic techniques. First, the forbidden D (3)Sigma(u) (+)-X (1)Sigma(g) (+) transition is observed for the first time via the (0,0) band of (14)N(2) and the (1,0) band of (15)N(2), using 1 extreme-ultraviolet +1 ultraviolet two-photon-ionization laser spectroscopy. Second, the Rydberg-Rydberg transition D (3)Sigma(u) (+)-E (3)Sigma(g) (+) is studied using near-infrared diode-laser photoabsorption spectroscopy, thus extending the previous measurements of Kanamori et al. [J. Chem. Phys. 95, 80 (1991)], to higher transition energies, and thereby revealing the (2,2) and (3,3) bands. The combined results show that the D(v=0-3) levels exhibit rapidly increasing rotational predissociation as v increases, spanning nearly four orders of magnitude. The D-state level structure and rotational predissociation signature are explained by means of a coupled-channels model which considers the electrostatically coupled (3)Pi(u) Rydberg-valence manifold, together with a pure-precession L-uncoupling rotational interaction between the 3psigma(u)D (3)Sigma(u) (+) and 3ppi(u)G (3)Pi(u) Rydberg p-complex components.

Observation of a new electronic state of CO perturbing WΠ1(v=1)

We observe photoabsorption of the W(1) ← X(0) band in five carbon monoxide isotopologues with a vacuum-ultraviolet Fourier-transform spectrometer and a synchrotron radiation source. We deduce transition energies, integrated cross sections, and natural linewidths of the observed rotational transitions and find a perturbation affecting these. Following a deperturbation analysis of all five isotopologues, the perturbing state is assigned to the v = 0 level of a previously unobserved (1)Π state predicted by ab initio calculations to occur with the correct symmetry and equilibrium internuclear distance. We label this new state E″ (1)Π. Both of the interacting levels W(1) and E″(0) are predissociated, leading to dramatic interference effects in their corresponding linewidths.

Experimental verification of strong rotational dependence of fluorescence and predissociation yield in the b 1Πu(v = 1) level of 14N2

New, rotationally resolved fluorescence-excitation spectra confirm coupled-channel Schrödinger-equation predictions of strong rotational dependence of the fluorescence and predissociation yields in the b(v = 1) level of (14)N(2).