fit_tscan

fit osc: fitting residual of experimental time trace spectrum data with the convolution of the sum of damped oscilliation and irf function There are three types of irf function (gaussian, cauchy, pseudo voigt) It uses lmfit python package to fitting residual of time trace data and estimates error bound of irf parameter, lifetime constants and period of vibrations. To calculate the contribution of each damped oscilliation component, it solve least linear square problem via scipy linalg lstsq module.

Note

  • The number of tau, period and phase parameter should be same

  • The number of time zero should be same as the number of residual scan file to fit.

  • phase should be confined in [-\(\pi/2\), \(\pi/2\)] (\(\pi\) ~ 3.14)

  • If you set shape of irf to pseudo voigt (pv), then you should provide two full width at half maximum value for gaussian and cauchy parts, respectively.

usage: fit_osc.py [-h] [–irf {g,c,pv}] [–fwhm_G FWHM_G] [–fwhm_L FWHM_L] [-t0 TIME_ZEROS [TIME_ZEROS …]] [-t0f TIME_ZEROS_FILE] [–tau TAU [TAU …]] [–period PERIOD [PERIOD …]] [–phase PHASE [PHASE …]] [–fix_irf] [–fix_t0] [–slow] [-o OUT] prefix

  • positional arguments:

    • prefix prefix for tscan files It will read prefix_i.txt

  • optional arguments:

    • -h, –help show this help message and exit

    • –irf {g,c,pv} shape of instrument response function

    1. g: gaussian distribution

    2. c: cauchy distribution

    3. pv: pseudo voigt profile, linear combination of gaussian distribution and cauchy distribution pv = eta*c+(1-eta)*g the mixing parameter is fixed according to Journal of Applied Crystallography. 33 (6): 1311–1316.

    • –fwhm_G FWHM_G full width at half maximum for gaussian shape It should not used when you set cauchy irf function

    • –fwhm_L FWHM_L full width at half maximum for cauchy shape It should not used when you did not set irf or use gaussian irf function

    • -t0 TIME_ZEROS [TIME_ZEROS …], –time_zeros TIME_ZEROS [TIME_ZEROS …] time zeros for each tscan

    • -t0f TIME_ZEROS_FILE, –time_zeros_file TIME_ZEROS_FILE filename for time zeros of each tscan

    • –tau [TAU [TAU …]] lifetime of each component

    • –period PERIOD [PERIOD …] period of the vibration of each component

    • –phase PHASE [PHASE …] phase factor of each damped oscilliation component

    • –fix_irf fix irf parameter (fwhm_G, fwhm_L) during fitting process

    • –fix_t0 fix time zero during fitting process

    • –slow use slower but robust global optimization algorithm

    • -o OUT, –out OUT prefix for output files

Parameter bound scheme

  • fwhm: temporal width of x-ray pulse

    • lower bound: 0.5*fwhm_init

    • upper bound: 2*fwhm_init

  • t_0: timezero for each scan

    • lower bound: t_0 - 2*fwhm_init

    • upper bound: t_0 + 2*fwhm_init

  • tau: life_time of each component

    • if tau < 0.1

      • lower bound: tau/2

      • upper bound: 1

    • if 0.1 < tau < 10

      • lower bound: 0.05

      • upper bound: 100

    • if 10 < tau < 100

      • lower bound: 5

      • upper bound: 500

    • if 100 < tau < 1000

      • lower bound: 50

      • upper bound: 2000

    • if 1000 < tau < 5000 then

      • lower bound: 500

      • upper bound: 10000

    • if 5000 < tau < 50000 then

      • lower bound: 2500

      • upper bound: 100000

    • if 50000 < tau < 500000 then

      • lower bound: 25000

      • upper bound: 1000000

    • if 500000 < tau < 1000000 then

      • lower bound: 250000

      • upper bound: 2000000

    • if 1000000 < tau then

      • lower bound: tau/4

      • upper bound: 4*tau

Mixing parameter eta

For pseudo voigt IRF function, mixing parameter eta is guessed to

\[\begin{equation*} \eta = 1.36603({fwhm}_L/f)-0.47719({fwhm}_L/f)^2+0.11116({fwhm}_L/f)^3 \end{equation*}\]

where

\[\begin{align*} f &= ({fwhm}_G^5+2.69269{fwhm}_G^4{fwhm}_L+2.42843{fwhm}_G^3{fwhm}_L^2 \\ &+ 4.47163{fwhm}_G^2{fwhm}_L^3+0.07842{fwhm}_G{fwhm}_L^4 \\ &+ {fwhm}_L^5)^{1/5} \end{align*}\]

This guess is according to J. Appl. Cryst. (2000). 33, 1311-1316