Seminar by Dr. Pradipta Samanta, Max Planck Institute for Solid State Research, Stuttgart, Germany on "Molecular properties using multi-reference coupled cluster methods"
05 Dec 2019
Seminar Room #350
Talk Title : "Molecular properties using multi-reference coupled cluster methods"
Abstract
An accurate calculation of molecular properties is an important aspect in quantum chemistry.Among the theoretical frameworks present to calculate molecular properties, response theory isthe most general one as it produces both time-independent as well as time-dependent properties.Response theory, in its perturbative framework, calculates the effect of an external periodicperturbation, such as electromagnetic field, on an electronic state. As it acts on the top of anelectronic structure method, the accuracy of results obtained from the response theory dependson the accuracy of the underlying electronic structure method. In this work, a linear variant ofthe response theory, known as the linear response (LR) theory, is formulated for the internallycontracted multi-reference coupled cluster (ic-MRCC) method with an aim to calculate highlyaccurate properties for molecular systems with prominent multi-reference character.ic-MRCC has been developed and used successfully in recent years to calculate energies withvery high accuracy for different kinds of multi-reference systems such as open shell molecules,transition states and bond dissociation. Formulation of a response theory is more challengingfor ic-MRCC as it is a non-variational method and, therefore, it requires a time-dependent La-grangian, involving new wave function parameters, to be formed. The formulation also involvessubsequent solutions of these wave function parameters and their higher order counterparts.The linear response theory for ic-MRCC (ic-MRCC-LR) has been applied to calculate differentfirst and second order electrical properties, such as dipole moments, static and dynamic dipole-polarizabillities, quadrupole moments, and electric field gradients, along with spin-dependentproperties, such as hyperfine coupling constants. Calculation of dynamic dipole-polarizabilityproduces poles those correspond to the energies of each excited states of a molecular system.This leads to an equation for the direct calculation of excitation energies as an alternative to theequation of motion (EOM) approach. Therefore, excitation energies have also been calculatedfor several molecules and compared with the results obtained from other quantum chemicalmethods. The results presented in this work show the accuracy of the ic-MRCC method whenextended beyond the calculation of energies for multi-reference systems.
