Vibronic Coupling

Tools for analysing vibronic coupling effects.

Huang-Rhys factors

The huang_rhys.py script is used for computing Huang-Rhys (HR) factors, which quantify the electron-phonon coupling between the ground and excited state geometries of a molecule along vibrational normal modes. It also calculates the reorganization energy, representing the nuclear reconfiguration cost during electronic transitions. The computed data are saved to an output file, which can be subsequently used as input for the fc_mini.py script.

To get detailed information about how to use this script, one can run the help command in the terminal:

huang_rhys.py -h

This command will display a comprehensive usage guide, including:

A brief description of the script’s purpose (computing Huang-Rhys parameters and reorganization energies).

Required Arguments: Ground state, Excited-state geometry file, Selection of vibrational molden files for ground or excited state (-g or -e).

Other options: File format type (-t), Display options for top vibrational modes by Huang-Rhys factors or reorganization energies, plotting and saving output options.

usage: huang_rhys.py [-h] (-g GS_VIB | -e ES_VIB) [-t FILETYPE] [-s N] [-l N] [-p PNGFILE] gs_file es_file

Compute Huang-Rhys parameters and reorganization energies.

positional arguments:
 gs_file               Ground state geometry file (e.g., gs.xyz)
 es_file               Excited-state geometry file (e.g., es.xyz)


options:
  -h, --help            show this help message and exit
  -g GS_VIB, --vib_gs GS_VIB
                     Ground-state vibrational Molden file (default)
  -e ES_VIB, --vib_es ES_VIB
                     Excited-state vibrational Molden file
  -t FILETYPE, --filetype FILETYPE
                     Filetype of structure files (default: xyz)
  -s N, --topS N        Show top N modes with highest Huang-Rhys factors
  -l N, --topLambda N   Show top N modes with highest reorganization energies
  -p PNGFILE, --plot PNGFILE
                     Plot Huang-Rhys spectrum and save to file

Example

huang_rhys.py GS.xyz ES.xyz -e freq.molden -s 10 -l 10 -p huang_rhys.png

Franck-Condon Spectrum

A Franck–Condon (FC) spectrum simulates the vibronic structure (combined electronic and vibrational transitions) of a molecule’s optical absorption or emission process. The fc_mini.py script is used for simulating a vibronic (Franck–Condon) progression spectrum based on Huang–Rhys factors, using a Gaussian line shape to broaden the discrete transitions.

Before running this script, a file containing vibrational mode data is necessary. This is generated by huang_rhys.py script. The file should have at least three columns - Mode, Frequency and Huang-Rhys Factor.

Example:

fc_mini.py hr.txt

After launching the script, the user is prompted to select the type of spectrum (absorption or emission) and input several parameters. It interactively guides the user through parameter selection, and produces numerical data and graphs.

To define the system, the user needs to specify

• Adiabatic energy in Hartree units

• Oscillator strength

• Refractive index of the solvent

The two main input parameters that describe the operation of the code are

• Minimum vibrational frequency in cm^-1 (w_min)

• Minimum Huang-Rhys factor value (S_min)

Modes, whose wave number is above w_min and whose Huang-Rhys factor is above S_min, are chosen for the Franck-Condon treatment. Any other modes are treated via semi-classical broadening.

To get a more accurate (but more computationally involved) spectrum, lower w_min and/or S_min.

Normal mode displacement

Displace a molecular structure along a normal mode.

add_normal_mode.py <in_struc> <out_struc> <vib_file> <nm_ind> <disp> [<type>]