Theoretical characterization of dimethyl carbonate at low temperatures.

Highly correlated ab initio methods (CCSD(T) and RCCSD(T)-F12) are employed for the spectroscopic characterization of the gas phase of dimethyl carbonate (DMC) at low temperatures. DMC, a relevant molecule for atmospheric and astrochemical studies, shows only two conformers, cis-cis and trans-cis, respectively, of C2v and Cs symmetries. cis-cis-DMC represents the most stable form. Using RCCSD(T)-F12 theory, the two sets of equilibrium rotational constants have been computed to be Ae = 10 493.15 MHz, Be = 2399.22 MHz, and Ce = 2001.78 MHz (cis-cis) and to be Ae = 6585.16 MHz, Be = 3009.04 MHz, and Ce = 2120.36 MHz (trans-cis). Centrifugal distortions constants and anharmonic frequencies for all of the vibrational modes are provided. Fermi displacements are predicted. The minimum energy pathway for the cis-cis → trans-cis interconversion process is restricted by a barrier of ∼3500 cm(-1). DMC displays internal rotation of two methyl groups. If the nonrigidity is considered, the molecule can be classified in the G36 (cis-cis) and the G18 (trans-cis) symmetry groups. For cis-cis-DMC, both internal tops are equivalent, and the torsional motions are restricted by V3 potential energy barriers of 384.7 cm(-1). trans-cis-DMC shows two different V3 barriers of 631.53 and 382.6 cm(-1). The far-infrared spectra linked to the torsional motion of both conformers are analyzed independently using a variational procedure and a two-dimensional flexible model. In cis-cis-DMC, the ground vibrational state splits into nine components: one nondegenerate, 0.000 cm(-1) (A1), four quadruply degenerate, 0.012 cm(-1) (G), and four doubly degenerate 0.024 cm(-1) (E1 and E3). The methyl torsional fundamentals are obtained to lie at 140.274 cm(-1) (ν15) and 132.564 cm(-1) (ν30).

Information-processing under incremental levels of physical loads: comparing racquet to combat sports.

AIM: Skillful performance in combat and racquet sports consists of proficient technique accompanied with efficient information-processing while engaged in moderate to high physical effort. This study examined information processing and decision-making using simple reaction time (SRT) and choice reaction time (CRT) paradigms in athletes of combat sports and racquet ball games while undergoing incrementally increasing physical effort ranging from low to high intensities. METHODS: Forty national level experienced athletics in the sports of tennis, table tennis, fencing, and boxing were selected for this study. Each subject performed both simple (SRT) and four-choice reaction time (4-CRT) tasks at rest, and while pedaling on a cycle ergometer at 20%, 40%, 60%, and 80% of their own maximal aerobic power (Pmax). RESULTS: RM MANCOVA revealed significant sport-type by physical load interaction effect mainly on CRT. Least significant difference (LSD) posthoc contrasts indicated that fencers and tennis players process information faster with incrementally increasing workload, while different patterns were obtained for boxers and table-tennis players. The error rate remained stable for each sport type over all conditions. Between-sport differences in SRT and CRT among the athletes were also noted. CONCLUSIONS: Findings provide evidence that the 4-CRT is a task that more closely corresponds to the original task athletes are familiar with and utilize in their practices and competitions. However, additional tests that mimic the real world experiences of each sport must be developed and used to capture the nature of information processing and response-selection in specific sports.

Simple and choice reaction times under varying levels of physical load in high skilled fencers.

AIM: Fencing requires rapid and accurate decision-making while competing and experiencing gradual perceived effort. This study examined the linkage between physical effort, simple reaction time and choice reaction time in fencers and non-fencer subjects. METHODS: Two age-matched groups participated in this experiment: 12 professional fencers and 12 sedentary subjects. Each subject performed both simple (SRT) and choice reaction time (CRT) tasks at rest, and while pedaling on a cycle ergometer at 20%, 40%, 60%, and 80% of their own maximal aerobic power (Pmax). RESULTS: At rest, no significant differences were found between experts and sedentary subjects neither in SRT nor CRT. The fencers showed shorter CRTs at 40%, 60% and 80% of Pmax compared to those measured at rest. In contrast, SRTs did not vary as a function of effort level. In sedentary subjects, workload did not affect SRTs and CRT. Moreover, the error rate remained stable for each group over all conditions. CONCLUSIONS: Current results showed that physical load results in enhancing information processing as measured by CRT without affecting SRT. The data provides evidence that aerobic exercise enhances attentional capability in fencers who are used to process information under similar physical conditions, but not in sedentary subjects unfamiliar to this environment. Exercise induces arousal that supports alertness to external environmental stimuli in highly trained athletes.