What is OpenRSP?

OpenRSP is a program library that uses recursive routines to identify and assemble contributions to response properties - that is, molecular properties as they are expressed in the theory called “response theory” from theoretical chemistry.

The name of OpenRSP reflects the following features:

  • It is a library for the Open-ended calculation of ReSPonse properties: It can be used for the calculation of reponse properties to arbitrary order.
  • It is Open-source and is publicly available under the LGPL v2.1 license.
  • It has an application programming interface that Opens it to connection with other programs that wish to make use of its functionality.

What are response properties?

Response properties describe how fundamental properties of a molecular system respond to external influences like subjection to an electromagnetic field or displacement of the atomic nuclei. They and related properties are essential for the description of spectroscopic processes and molecular characteristics like infrared spectroscopy, Raman scattering, multiphoton absorption and vibrational energy levels. If you have ever done computational work on the molecular level for phenomena in this category, chances are that response properties were involved at some stage of the calculation.

Response properties can be categorized by their order, that is, the “number of influences” that were taken into consideration for a given property. The first such order is called linear response and contains much-used properties like the electric dipole polarizability - i.e. the first-order change to the molecular dipole moment in the presence of an electric field - or the Hessian matrix of nuclear geometric displacements - i.e. the change in the molecular gradient that would result from displacing each coordinate of the molecular geometry.

Higher orders of response properties describe the changes that the fundamental molecular property would undergo upon subjection to more than one external influence, or upon higher-order interactions with the same influence. Examples of such properties are the geometric gradient of the electric dipole polarizability - essential for the description of vibrational Raman spectra - or the cubic and quartic force constants, i.e. the third- and fourth-order derivatives of the molecular energy with respect to geometrical displacements - which may be used to calculate corrections to a description of the vibrational energy levels stemming from the geometric Hessian.

Why use OpenRSP?

By its recursive structure, OpenRSP makes it possible to calculate response properties of arbitrary complexity in an analytical manner, not resorting to numerical schemes like finite difference methods in the calculation. Compared to analytical methods, numerical approaches may be associated with a greater degree of uncertainty related to accuracy and practical feasibility of the calculation, and we therefore think that analytical calculation should be used whenever it is practical.

Today’s programs written for the calculation of response properties may either not have a recursive structure, or may use numerical methods to different extents, or both. In the cases where existing programs use an analytical approach, they may either be not recursive (which typically means that a new program routine must be written for each new property for which calculation is desired), or they may only be usable for a limited category of properties. As the complexity of the expressions that must be evaluated in an analytical approach to yield the desired response property increases rapidly with the order of response, such analytic calculation of high-order response properties can quickly become a very complicated task and the implementation of ad hoc program routines for their calculation may be intractable at higher orders.

The structure of OpenRSP, using recursion as a core tool, solves the task of identifying and assembling contributions to response properties “once and for all”. When combined with program libraries that can provide the contributions that OpenRSP identifies, any response property can be calculated fully analytically as long as those libraries can provide the necessary contributions. We note, however, that the present version of the code is still awaiting the completion of functionality to handle perturbations that both change the basis set and have a nonzero frequency associated with them, but that such extension is within the scope of the present underlying theory.