ABSTRACT
DL_FFLUX is a force field based on quantum chemical topology that can perform molecular dynamics for flexible molecules endowed with polarizable atomic multipole moments (up to hexadecapole). Using the machine learning method kriging (aka Gaussian process regression), DL_FFLUX has access to atomic properties (energy, charge, dipole moment, etc.) with quantum mechanical accuracy. Newly optimized and parallelized using domain decomposition Message Passing Interface (MPI), DL_FFLUX is now able to deliver this rigorous methodology at scale while still in reasonable time frames. DL_FFLUX is delivered as an add-on to the widely distributed molecular dynamics code DL_POLY 4.08. For the systems studied here (103-105 atoms), DL_FFLUX is shown to add minimal computational cost to the standard DL_POLY package. In fact, the optimization of the electrostatics in DL_FFLUX means that, when high-rank multipole moments are enabled, DL_FFLUX is up to 1.25× faster than standard DL_POLY. The parallel DL_FFLUX preserves the quality of the scaling of MPI implementation in standard DL_POLY. For the first time, it is feasible to use the full capability of DL_FFLUX to study systems that are large enough to be of real-world interest. For example, a fully flexible, high-rank polarized (up to and including quadrupole moments) 1 ns simulation of a system of 10â¯125 atoms (3375 water molecules) takes 30 h (wall time) on 18 cores.
ABSTRACT
Official rankings are the most common measure of success in professional women's tennis. Despite their importance for earning potential and tournament seeding, little is known about ranking trajectories of female players and their influence on career success. Our objective was to conduct a comprehensive study of the career progression of elite female tennis talent. The study examined the ranking trajectories of the top 250 female professionals between 1990 and 2015. Using regression modelling of yearly peak rankings, we found a strong association between the shape of the ranking trajectory and the highest career ranking earned. Players with the highest career peak ranking were the youngest when first ranked. For example, top 10 players were first ranked at age 15.5 years (99% CI = 14.8-15.9), 1.2 years (99% CI = 0.8-1.5) earlier than top 51-100 players. Top 10 players were also ranked in the top 100 longer than other players, holding a top 100 ranking until a mean age of 29.0 years (99% CI = 27.8-30.3) compared with age 24.4 years (99% CI = 23.7-25.2) for top 51-100 players. Ranking trajectories were more distinct with respect to player age than years from first ranking. The present study's findings will be instructive for players, coaches, and administrators in setting goals and assessing athlete development in women's tennis.
Subject(s)
Achievement , Aptitude , Tennis , Adolescent , Adult , Athletes , Athletic Performance , Female , Humans , Young AdultABSTRACT
The high-resolution (0.001 cm(-1)) spectrum of thiirane has been recorded at the far-infrared beamline at the Australian synchrotron between 760-400 cm(-1) and 170-10 cm(-1). Ro-vibrational transitions of the highly Coriolis coupled ν(5) (628.1 cm(-1)) and ν(15) (669.7 cm(-1)) fundamentals, as well as pure rotational far-IR transitions have been assigned, and rotational, centrifugal distortion, and Coriolis interaction parameters determined. ν(15) gains the vast majority of its intensity from an interesting Coriolis intensity stealing mechanism, which is also outlined.
Subject(s)
Sulfides/chemistry , Synchrotrons , Quantum Theory , Spectroscopy, Fourier Transform InfraredABSTRACT
High-resolution FTIR spectra of the short lived species ketenimine have been recorded in the region 700-1300 cm(-1) and over 1500 transitions of the ν(10) and ν(6) modes have been assigned. Effective rotational and centrifugal distortion parameters for the v(10) = 1 and v(6) = 1 (excluding K(a) = 5) states were determined by co-fitting transitions, and treating strong a- and c-axis Coriolis interactions between them. Other perturbations attributed to interactions with the v(8) = 2 and v(12) = 1 + v(8) = 1 dark-states were also observed and treated. The ν(10) transitions are predicted to be inherently very weak, but are enhanced by an intensity stealing effect with the highly IR active ν(6) mode. A mechanism for this intensity stealing in ketenimine is also detailed.
ABSTRACT
High resolution FTIR spectra of the short lived species ketenimine have been recorded in the regions 390-1300 cm(-1) and 20-110 cm(-1) using synchrotron radiation. Two thousand six hundred sixty transitions of the ν(7) band centered at 693 cm(-1) and 126 far-IR rotational transitions have been assigned. Rotational and centrifugal distortion parameters for the ν(7) mode were determined and local Fermi and b-axis Coriolis interactions with 2ν(12) are treated. A further refinement of the ground state, ν(12) and ν(8) parameters was also achieved, including the treatment of previously unrecognized ac-axis and ab-axis second order perturbations to the ground state.
ABSTRACT
High resolution FTIR spectra have been recorded in the region 250-770 cm(-1) using synchrotron radiation and over 2000 transitions to the ν(8) and ν(12) states of the short lived species ketenimine have been assigned. Ground state combination differences combined with published microwave transitions were used to refine the constants for the ground vibrational state. Rotational and centrifugal distortion parameters for the v(8) = 1 and v(12) = 1 levels were determined by co-fitting transitions, and treating a strong a-axis Coriolis interaction. Selection rules for the observed ν(12) transitions indicate that they arise solely from "perturbation allowed" intensity resulting from this Coriolis interaction.
ABSTRACT
The current state of the art in recording and analyzing rotationally resolved vibration-rotation bands of atmospheric pollutant halocarbon species is reviewed. It is shown that in order to obtain molecular constants of sufficient accuracy to simulate the vibration-rotation structure over the range of atmospheric temperatures, it is necessary to obtain spectra at a range of temperatures using static cooling cells, supersonic jet expansions, and collisional cooling devices; employ sophisticated pattern recognition and analysis software; assign and fit spectral perturbations; and use spectral simulation and digital spectral subtraction (SASSI) to further simplify spectral bands for analysis. To demonstrate the techniques, an analysis of the ν(5) band of CH(37)ClF(2) in natural abundance is presented.
