spectrum¶
- psi4.driver.p4util.spectrum(*, poles, residues, kind='opa', lineshape='gaussian', gamma=0.2, npoints=5000, out_units='nm')[source]¶
One-photon absorption (OPA) or electronic circular dichroism (ECD) spectra with phenomenological line broadening.
This function gives arrays of values ready to be plotted as OPA spectrum:
\[\varepsilon(\omega) = \frac{4\pi^{2}N_{\mathrm{A}}\omega}{3\times 1000\times \ln(10) (4 \pi \epsilon_{0}) n \hbar c} \sum_{i \rightarrow j}g_{ij}(\omega)|\mathbf{\mu}_{ij}|^{2}\]or ECD spectrum:
\[\Delta\varepsilon(\omega) = \frac{16\pi^{2}N_{\mathrm{A}}\omega}{3\times 1000\times \ln(10) (4 \pi \epsilon_{0}) n \hbar c^{2}} \sum_{i \rightarrow j}g_{ij}(\omega)\Im(\mathbf{\mu}_{ij}\cdot\mathbf{m}_{ij})\]in macroscopic units of \(\mathrm{L}\cdot\mathrm{mol}^{-1}\cdot\mathrm{cm}^{-1}\). The lineshape function \(g_{ij}(\omega)\) with phenomenological broadening \(\gamma\) is used for the convolution of the infinitely narrow results from a linear response calculation.
- Parameters:
poles (
Union[List[float],ndarray]) – Poles of the response function, i.e. the excitation energies. These are expected in atomic units of angular frequency.residues (
Union[List[float],ndarray]) – Residues of the linear response functions, i.e. transition dipole moments (OPA) and rotatory strengths (ECD). These are expected in atomic units.kind (
str) – {“opa”, “ecd”} Which kind of spectrum to generate, one-photon absorption (“opa”) or electronic circular dichroism (“ecd”). Default is opa.lineshape (
str) – {“gaussian”, “lorentzian”} The lineshape function to use in the fitting. Default is gaussian.gamma (
float) – Full width at half maximum of the lineshape function. Default is 0.2 au of angular frequency. This value is expected in atomic units of angular frequency.npoints (
int) – How many points to generate for the x axis. Default is 5000.out_units (
str) –Units for the output array x, the x axis of the spectrum plot. Default is wavelengths in nanometers. Valid (and case-insensitive) values for the units are:
au atomic units of angular frequency
Eh atomic units of energy
eV
nm
THz
- Returns:
spectrum – The fitted electronic absorption spectrum, with units for the x axis specified by the out_units parameter. This is a dictionary containing the convoluted (key: convolution) and the infinitely narrow spectra (key: sticks).
{"convolution": {"x": np.ndarray, "y": np.ndarray}, "sticks": {"poles": np.ndarray, "residues": np.ndarray}}
- Return type:
Dict[str, numpy.ndarray]
Notes
Conversion of the broadening parameter \(\gamma\). The lineshape functions are formulated as functions of the angular frequency \(\omega\). When converting to other physical quantities, the broadening parameter has to be modified accordingly. If \(\gamma_{\omega}\) is the chosen broadening parameter then:
Wavelength: \(gamma_{\lambda} = \frac{\lambda_{ij}^{2}}{2\pi c}\gamma_{\omega}\)
Frequency: \(gamma_{\nu} = \frac{\gamma_{\omega}}{2\pi}\)
Energy: \(gamma_{E} = \gamma_{\omega}\hbar\)
References
A. Rizzo, S. Coriani, K. Ruud, “Response Function Theory Computational Approaches to Linear and Nonlinear Optical Spectroscopy”. In Computational Strategies for Spectroscopy. https://doi.org/10.1002/9781118008720.ch2
