Electronic spectroscopy of thiones

The phosphorescence excitation spectra of two thiones, 4-H-1-xanthione (XT) and 4-H-1-pyrane-4-thione (PT), cooled in a supersonic jet were investigated. The vibronic lineshape of the T1z origin of PT measured by cavity ring-down spectroscopy is considered and the excited state rotational constants are calculated. For XT the 3A2(nπ* ) → X1A1 phosphorescence excitation spectrum was investigated in the region 14900-17600 cm-1. The structure observed is shown to be due to the T1← S0 absorption and an assignment in terms of the vibronic structure of the band is proposed. A previous assignment of the S1 ← S0 origin is considered and the transition involved is shown to be most probably due to the absorption of a vibronic tiplet state T1z,v7. An alternative but tentative assignment of the S1,0 ←S0,0 transition is suggested. In the case of PT the phosphorescence excitation spectrum was investigated in the region of the 1A2(ππ*) ← X1A1 absorption band between 27300 and 28800 cm-1. The spectrum exhibits complex features which are typical for the strong vibronic coupling case of two adjacent electronic states. The observed intermediate level structure was attributed to the coupling with a lower lying dark electronic state 1B1(nπ*2), whose origin was estimated to be ~ 825 - 1025 cm-1 below the origin of 1A2(ππ*)0. Consequences of the vibronic coupling on the decay dynamics of 1A2(ππ*) as well as tentative assignments of vibronic transitions 1A2(ππ*)v ← X1A1 are also discussed. In the T1z ← S0 cavity ring-down absorption spectrum of PT, the vibronic lineshape of the T1z origin is analysed. As the T1z line is separated from the T1x,1y lines by a large zero-field splitting it is possible to use an Asyrot-like program to calculate the vibrational-rotational parameters determining the lineshape. It is shown that PT is non-planar in the first excited triplet state and the lineshape is composed of a mixture of A-type and C-type bandshapes. The non-planarity of PT is discussed.

Study abroad and complexity, accuracy and fluency (CAF) development: a longitudinal investigation of French and Chinese Learners of L2 English

This longitudinal study tracked third-level French (n=10) and Chinese (n=7) learners of English as a second language (L2) during an eight-month study abroad (SA) period at an Irish university. The investigation sought to determine whether there was a significant relationship between length of stay (LoS) abroad and gains in the learners' oral complexity, accuracy and fluency (CAF), what the relationship was between these three language constructs and whether the two learner groups would experience similar paths to development. Additionally, the study also investigated whether specific reported out-of-class contact with the L2 was implicated in oral CAF gains. Oral data were collected at three equidistant time points; at the beginning of SA (T1), midway through the SA sojourn (T2) and at the end (T3), allowing for a comparison of CAF gains arising during one semester abroad to those arising during a subsequent semester. Data were collected using Sociolinguistic Interviews (Labov, 1984) and adapted versions of the Language Contact Profile (Freed et al., 2004). Overall, the results point to LoS abroad as a highly influential variable in gains to be expected in oral CAF during SA. While one semester in the TL country was not enough to foster statistically significant improvement in any of the CAF measures employed, significant improvement was found during the second semester of SA. Significant differences were also revealed between the two learner groups. Finally, significant correlations, some positive, some negative, were found between gains in CAF and specific usage of the L2. All in all, the disaggregation of the group data clearly illustrates, in line with other recent enquiries (e.g. Wright and Cong, 2014) that each individual learner's path to CAF development was unique and highly individualised, thus providing strong evidence for the recent claim that SLA is "an individualized nonlinear endeavor" (Polat and Kim, 2014: 186).